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Contents
Articles
Overview
Alchemy
Chemistry
19
History of chemistry
33
43
Timeline of chemistry
47
65
Atom
65
Atomic nucleus
86
Proton
92
Neutron
98
Electron
108
Chemical element
131
Isotope
149
Ion
158
Molecule
164
Chemical compound
167
Chemical substance
170
175
Phases
175
Gas
179
Liquid
191
Solid
197
Periodic table
209
Valence electron
209
Periodic table
212
Periodic trends
222
Period
224
Group
229
Chemical concepts
231
Ionic radius
231
240
Electronegativity
243
Mole
252
Lewis structure
256
Chemical bond
260
Chemical reactions
269
Chemical reaction
269
Chemical law
285
Solution
286
Acid
289
Reductionoxidation
300
Miscellaneous
308
Etymology
308
Chemical industry
310
References
Article Sources and Contributors
318
328
Article Licenses
License
333
Overview
Alchemy
Alchemy is an influential philosophical tradition whose early
practitioners claims to profound powers were known from antiquity.
The defining objectives of alchemy are varied; these include the
creation of the fabled philosopher's stone possessing powers including
the capability of turning base metals into the noble metals gold or
silver, as well as an elixir of life conferring youth and immortality. In
general alchemists believe in a natural and symbolic unity of humanity
with the cosmos. Lately western alchemy has become recognized as
the proto-typical protoscience presaging the seminal western sciences
such as chemistry and medicine. Alchemists nurtured a framework of
theory, terminology, experimental process and basic lab techniques
still recognizable today. But alchemy differs from modern science in
the inclusion of Hermetic principles and practices related to
mythology, religion, and spirituality.
Overview
Alchemy
It is a popular belief that Alchemists made contributions to the "chemical" industries of the dayore testing and
refining, metalworking, production of gunpowder, ink, dyes, paints, cosmetics, leather tanning, ceramics, glass
manufacture, preparation of extracts, liquors, and so on (it seems that the preparation of aqua vitae, the "water of
life", was a fairly popular "experiment" among European alchemists). Alchemists contributed distillation to Western
Europe. The attempts of alchemists to arrange information on substances, so as to clarify and anticipate the products
of their chemical reactions, resulted in early conceptions of chemical elements and the first rudimentary periodic
tables. They learned how to extract metals from ores, and how to compose many types of inorganic acids and bases.
During the 17th century, practical alchemy started to evolve into modern chemistry,[11] as it was renamed by Robert
Boyle, the "father of modern chemistry".[12] In his book, The Skeptical Chymist, Boyle attacked Paracelsus and the
natural philosophy of Aristotle, which was taught at universities. However, Boyle's biographers, in their emphasis
that he laid the foundations of modern chemistry, neglect how steadily he clung to the Scholastic sciences and to
Alchemy, in theory, practice and doctrine.[13] The decline of alchemy continued in the 18th century with the birth of
modern chemistry, which provided a more precise and reliable framework within a new view of the universe based
on rational materialism.
Relation to Hermeticism
In the eyes of a variety of esoteric and Hermetic practitioners, the heart of alchemy is spiritual. Transmutation of lead
into gold is presented as an analogy for personal transmutation, purification, and perfection.[4] This approach is often
termed 'spiritual', 'esoteric', or 'internal' alchemy.
Early alchemists, such as Zosimos of Panopolis (c. 300 A.D.), highlight the spiritual nature of the alchemical quest,
symbolic of a religious regeneration of the human soul.[14] This approach continued in the Middle Ages, as
metaphysical aspects, substances, physical states, and material processes were used as metaphors for spiritual
entities, spiritual states, and, ultimately, transformation. In this sense, the literal meanings of 'Alchemical Formulas'
were a blind, hiding their true spiritual philosophy. Practitioners and patrons such as Melchior Cibinensis and Pope
Innocent VIII existed within the ranks of the church, while Martin Luther applauded alchemy for its consistency with
Christian teachings.[15] Both the transmutation of common metals into gold and the universal panacea symbolized
evolution from an imperfect, diseased, corruptible, and ephemeral state towards a perfect, healthy, incorruptible, and
everlasting state; and the philosopher's stone then represented a mystic key that would make this evolution possible.
Applied to the alchemist himself, the twin goal symbolized his evolution from ignorance to enlightenment, and the
stone represented a hidden spiritual truth or power that would lead to that goal. In texts that are written according to
this view, the cryptic alchemical symbols, diagrams, and textual imagery of late alchemical works typically contain
multiple layers of meanings, allegories, and references to other equally cryptic works; and must be laboriously
decoded to discover their true meaning.
In his 1766 Alchemical Catechism, Thodore Henri de Tschudi denotes that the usage of the metals was a symbol:
Q. When the Philosophers speak of gold and silver, from which they extract their matter, are we to suppose that they refer to the vulgar gold
[16]
and silver? A. By no means; vulgar silver and gold are dead, while those of the Philosophers are full of life.
During the renaissance, alchemy broke into more distinct schools placing spiritual alchemists in high contrast with
those working with literal metals and chemicals.[17] While most spiritual alchemists also incorporate elements of
exotericism, examples of a purely spiritual alchemy can be traced back as far as the sixteenth century, when Jacob
Boehme used alchemical terminology in strictly mystical writings.[18] Another example can be found in the work of
Heinrich Khunrath (15601605) who viewed the process of transmutation as occurring within the alchemist's
soul.[17]
The recent work of Principe and Newman, seeks to reject the 'spiritual interpretation' of alchemy, stating it arose as a
product of the Victorian occult revival.[19] There is evidence to support that some classical alchemical sources were
Alchemy
adulterated during this time to give greater weight to the spiritual aspects of alchemy.[20] [21] Despite this, other
scholars such as Calian and Tilton reject this view as entirely historically inaccurate, drawing examples of historical
spiritual alchemy from Boehme, Isaac Newton, and Michael Maier.[22]
Etymology
The word alchemy derives from the Old French alquimie, which is from the Medieval Latin alchimia, and which is
in turn from the Arabic al-kimia (). This term itself is derived from the Ancient Greek chemeia () or
chemia ()[23] with the addition of the Arabic definite article al- ().[24] The ancient Greek word may have been
derived from[25] a version of the Egyptian name for Egypt, which was itself based on the Ancient Egyptian word
kme (hieroglyphic Khmi, black earth, as opposed to desert sand).[24] The word could also have originally derived
from chumeia () meaning "mixture" and referring to pharmaceutical chemistry.[26] With the later rise of
alchemy in Alexandria, the word may have derived from , and thus became spelled as , and the original
meaning forgotten.[27] The etymology is still open, and recent research indicates that the Egyptian derivation may be
valid.[28]
History
Alchemy covers several philosophical
traditions spanning some four millennia and
three continents. These traditions' general
penchant for cryptic and symbolic language
makes it hard to trace their mutual
influences and "genetic" relationships. One
can distinguish at least three major strands,
which appear to be largely independent, at
Extract and symbol key from a 17th century book on alchemy. The symbols used
least in their earlier stages: Chinese
have a one-to-one correspondence with symbols used in astrology at the time.
alchemy, centered in China and its zone of
cultural influence; Indian alchemy, centered around the Indian subcontinent; and Western alchemy, which occurred
around the Mediterranean and whose center has shifted over the millennia from Greco-Roman Egypt, to the Islamic
world, and finally medieval Europe. Chinese alchemy was closely connected to Taoism and Indian alchemy with the
Dharmic faiths, whereas Western alchemy developed its own philosophical system that was largely independent of,
but influenced by, various Western religions. It is still an open question whether these three strands share a common
origin, or to what extent they influenced each other.
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bodies first reveals itself in differentiated form."[40] Later alchemists extensively developed the mystical aspects of
this concept.
Alchemy coexisted alongside emerging Christianity. Lactantius believed Hermes Trismegistus had prophesied its
birth. Augustine (354430 CE) later affirmed this, but also condemned Trismegistus for idolatry.[41] Examples of
Pagan, Christian, and Jewish alchemists can be found during this period.
Most of the Greco-Roman alchemists preceding Zosimos are known only by pseudonyms, such as Moses, Isis,
Cleopatra, Democritus, and Ostanes. Others authors such as Komarios, and Chymes, we only know through
fragments of text. After 400 CE, Greek alchemical writers occupied themselves solely in commenting on the works
of these predecessors.[42] By the middle of the seventh century alchemy was almost an entirely mystical
discipline.[43] It was at that time that Khalid Ibn Yazid sparked its migration from Alexandria to the Islamic world,
facilitating the translation and preservation of Greek alchemical texts in the 8th and 9th centuries.[44]
To form an idea of the historical place of Jabirs 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 Jabirs 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
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6
is one of clearness and of an impressive unity. More than with the other Arab authors, one notes with him a
balance between theoretical teaching and practical teaching, between the `ilm and the `amal. In vain one would
seek in the Greek texts a work as systematic as that which is presented for example in the Book of Seventy.
Jabir himself clearly recognized and proclaimed the importance of experimentation as follows:
The first essential in chemistry is that thou shouldest perform practical work and conduct experiments, for he
who performs not practical work nor makes experiments will never attain to the least degree of mastery.[48]
Early Islamic chemists such as Jabir Ibn Hayyan ( in Arabic, Geberus in Latin; usually rendered in English
as Geber), Al-Kindi (Alkindus) and Muhammad ibn Zakarya Rzi (Rasis or Rhazes in Latin) contributed a number
of key chemical discoveries, such as the muriatic (hydrochloric acid), sulfuric and nitric acids, and more. The
discovery that aqua regia, a mixture of nitric and hydrochloric acids, could dissolve the noblest metal, gold, was to
fuel the imagination of alchemists for the next millennium.
Islamic philosophers also made great contributions to alchemical hermeticism. The most influential author in this
regard was arguably Jabir. Jabir's ultimate goal was Takwin, the artificial creation of life in the alchemical
laboratory, up to and including human life. He analyzed each Aristotelian element in terms of four basic qualities of
hotness, coldness, dryness, and moistness.[49] According to Jabir, in each metal two of these qualities were interior
and two were exterior. For example, lead was externally cold and dry, while gold was hot and moist. Thus, Jabir
theorized, by rearranging the qualities of one metal, a different metal would result.[49] By this reasoning, the search
for the philosopher's stone was introduced to Western alchemy. Jabir developed an elaborate numerology whereby
the root letters of a substance's name in Arabic, when treated with various transformations, held correspondences to
the element's physical properties.
The elemental system used in medieval alchemy also originated with Jabir. His original system consisted of seven
elements, which included the five classical elements (aether, air, earth, fire and water), in addition to two chemical
elements representing the metals: sulphur, the stone which burns, which characterized the principle of
combustibility, and mercury, which contained the idealized principle of metallic properties. Shortly thereafter, this
evolved into eight elements, with the Arabic concept of the three metallic principles: sulphur giving flammability or
combustion, mercury giving volatility and stability, and salt giving solidity.[50] The atomic theory of
corpuscularianism, where all physical bodies possess an inner and outer layer of minute particles or corpuscles, also
has its origins in the work of Jabir.[51]
During the 9th to 14th centuries, alchemical theories faced criticism from a variety of practical Muslim chemists,
including Ja'far al-Sadiq,[52] Alkindus,[53] Ab al-Rayhn al-Brn,[54] Avicenna[55] and Ibn Khaldun. In particular,
they wrote refutations against the idea of the transmutation of metals.
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correspondence with Pope Clement IV highlighted this integration, calling attention to the importance of alchemy to
the papacy.[61] Like the Greeks before him, Bacon acknowledged the division of alchemy into the practical and
theoretical. He notes that the theoretical lied outside the scope of Aristotle, the natural philosophers, and all Latin
writers of his time. The practical however, confirmed the theoretical through experiment, and Bacon advocated its
uses in natural science and medicine.[62]
Soon after Bacon, the influential work of Pseudo-Geber (sometimes identified as Paul of Taranto) appeared. His
Summa Perfectionis remained a staple summary of alchemical practice and theory through the medieval and
renaissance periods. It was notable for its inclusion of practical chemical operations alongside sulphur-mercury
theory, and the unusual clarity with which they were described.[63] By the end of the 13th century, alchemy had
developed into a fairly structured system of belief. Adepts believed in the macrocosm-microcosm theories of
Hermes, that is to say, they believed that processes that affect minerals and other substances could have an effect on
the human body (for example, if one could learn the secret of purifying gold, one could use the technique to purify
the human soul). They believed in the four elements and the four qualities as described above, and they had a strong
tradition of cloaking their written ideas in a labyrinth of coded jargon set with traps to mislead the uninitiated.
Finally, the alchemists practiced their art: they actively experimented with chemicals and made observations and
theories about how the universe operated. Their entire philosophy revolved around their belief that man's soul was
divided within himself after the fall of Adam. By purifying the two parts of man's soul, man could be reunited with
God.[64]
In the 14th century, alchemy became more accessible to Europeans outside the confines of Latin speaking
churchmen and scholars. Alchemical discourse shifted from scholarly philosophical debate to an exposed social
commentary on the alchemists themselves.[65] Dante, Piers the Ploughman, and Chaucer all painted unflattering
pictures of alchemists as thieves and liars. Pope John XXIIs 1317 edict, Spondent quas non exhibent forbade the
false promises of transmutation made by pseudo-alchemists.[66] In 1403, Henry IV of England banned the practice of
multiplying metals. These critiques and regulations centered more around pseudo-alchemical charlatanism than the
actual study of alchemy, which continued with an increasingly Christian tone. The 14th century saw the Christian
imagery of death and resurrection employed in the alchemical texts of Petrus Bonus, John of Rupescissa and in
works written in the name of Raymond Lull and Arnold of Villanova.[67]
Nicolas Flamel lived from 1330 to 1417 and would serve as the archetype for the next phase of alchemy. He was not
a religious scholar as were many of his predecessors, and his entire interest in the subject revolved around the pursuit
of the philosopher's stone. His work spends a great deal of time describing the processes and reactions, but never
actually gives the formula for carrying out the transmutations. Most of his work was aimed at gathering alchemical
knowledge that had existed before him, especially as regarded the philosopher's stone.[68] Though the historical
Flamel existed, the writings and legends assigned to him only appeared in 1612. Current scholarship suggests that
they are fictionanother example of the tradition of pseudepigraphy and allegory in alchemical writing.[69]
Through the late Middle Ages (13001500) alchemists were much like Flamel: they concentrated on looking for the
philosophers' stone. Bernard Trevisan and George Ripley made similar contributions in the 14th and 15th centuries .
Their cryptic allusions and symbolism led to wide variations in interpretation of the art.
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subject (Monas Hieroglyphica, 1564) influenced by the Kabbalah. Dee's associate Edward Kelley who claimed to
converse with angels through a crystal ball and to own a powder that would turn mercury into gold may have
been the source of the popular image of the alchemist-charlatan.
Rudolf II, Holy Roman Emperor, in the late 16th century, sponsored various alchemists in their work at his court in
Prague, one of which was a particular alchemist named Edward Kelley. Kelley had been a protegee of John Dee in
England.
Another lesser known alchemist was Michael Sendivogius (Micha Sdziwj, 15661636), a Polish alchemist,
philosopher, medical doctor and pioneer of chemistry. According to some accounts, he distilled oxygen in a lab
sometime around 1600, 170 years before Scheele and Priestley, by warming nitre (saltpetre). He thought of the gas
given off as "the elixir of life". Shortly after discovering this method, it is believed that Sendivogious taught his
technique to Cornelius Drebbel. In 1621, Drebbel practically applied this in a submarine.
Tycho Brahe (15461601), better known for his astronomical and astrological investigations, was also an alchemist.
He had a laboratory built for that purpose at his Uraniborg observatory/research institute.
Up to the 17th century, alchemy was practiced by scientists, such as Isaac Newton who devoted considerably more
of his writing to the study of alchemy (see Isaac Newton's occult studies) than he did to either optics or physics.
Other alchemists of the Western world who were eminent in their other studies include Roger Bacon, and Tycho
Brahe.
10
Alchemy
11
emphasis that he laid the foundations of modern chemistry, neglect how steadily he clung to the Scholastic sciences
and to Alchemy, in theory, practice and doctrine.[13] The decline of alchemy continued in the 18th century with the
birth of modern chemistry, which provided a more precise and reliable framework within a new view of the universe
based on rational materialism.
The words "alchemy" and "chemistry" were used interchangeably during most of the seventeenth century; only
during the eighteenth century was a distinction drawn rigidly between the two.[78] In the eighteen century, "alchemy"
was considered to be restricted to the realm of "gold making", leading to the popular belief that most, if not all,
alchemists were charlatans, and the tradition itself nothing more than a fraud.[79] The obscure and secretive writings
of the alchemists was used as a case by those who wished to forward a fraudulent and non-scientific opinion of
alchemy.[80] In order to protect the developing science of modern chemistry from the negative censure of which
alchemy was being subjected, academic writers during the scientific Enlightenment attempted, for the sake of
survival, to separate and divorce the "new" chemistry from the "old" practices of alchemy. This move was mostly
successful, and the consequences of this continued into the nineteenth and twentieth centuries, and even to the
present day.[81]
During the occult revival of the early nineteenth century, alchemy received new attention as an occult science.[82]
The esoteric or occultist school, which arose during the nineteenth century, held (and continues to hold) the view that
the substances and operations mentioned in alchemical literature are to be interpreted in a spiritual sense, and it
downplays the role of the alchemy as a practical tradition or protoscience.[83] This interpretation further forwarded
the view that alchemy is an art primarily concerned with spiritual enlightenment or illumination, as opposed to the
physical manipulation of apparatus and chemicals, and claims that the obscure language of the alchemical texts were
an allegorical guise for spiritual, moral or mystical processes.[84] In the first half of the 19th century, one established
chemist, Baron Carl Reichenbach, worked on concepts similar to the old alchemy, such as the Odic force, but his
research did not enter the mainstream of scientific discussion.
In the nineteenth century revival of alchemy, the two most seminal figures were Mary Anne Atwood, and Ethan
Allen Hitchcock who independently published similar works regarding spiritual alchemy. Both forwarded a
completely esoteric view of alchemy, as Atwood claimed: "No modern art or chemistry, notwithstanding all its
surreptitious claims, has any thing in common with Alchemy." [85] [86] Atwood's work influenced subsequent authors
of the occult revival including Eliphas Levi, Arthur Edward Waite, and Rudolf Steiner. Hitchcock, in his Remarks
Upon Alchymists (1855) attempted to make a case for his spiritual interpretation with his claim that the alchemists
wrote about a spiritual discipline under a materialistic guise in order to avoid accusations of blasphemy from the
church and state.
Thus, as science steadily continued to uncover and rationalize the clockwork of the universe, founded on its own
materialistic metaphysics, alchemy was left deprived of its chemical and medical connections but still incurably
burdened by them. Reduced to an arcane philosophical system, poorly connected to the material world, it suffered
the common fate of other esoteric disciplines such as astrology and Kabbalah: excluded from university curricula,
shunned by its former patrons, ostracized by scientists, and commonly viewed as the epitome of charlatanism and
superstition. These developments could be interpreted as part of a broader reaction in European intellectualism
against the Romantic movement of the preceding centuries.
Indian alchemy
According to Multhauf & Gilbert (2008):[87]
The oldest Indian writings, the Vedas (Hindu sacred scriptures), contain the same hints of alchemy that
are found in evidence from ancient China, namely vague references to a connection between gold and
long life. Mercury, which was so vital to alchemy everywhere, is first mentioned in the 4th- to
3rd-century-BC Artha-stra, about the same time it is encountered in China and in the West. Evidence
of the idea of transmuting base metals to gold appears in 2nd- to 5th-century-AD Buddhist texts, about
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12
the same time as in the West. Since Alexander the Great had invaded Ancient India in 325 BC, leaving a
Greek state (Gandhra) that long endured, the possibility exists that the Indians acquired the idea from
the Greeks, but it could have been the other way around.
Significant progress in alchemy was made in ancient India. Will Durant wrote in 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."
An 11th century Persian chemist and physician named Ab Rayhn Brn reported that they "have a science similar
to alchemy which is quite peculiar to them, which in Sanskrit is called Rasayna and in Persian Rasavtam. It means
the art of obtaining/manipulating Rasa: nectar, mercury, and juice. This art was restricted to certain operations,
metals, drugs, compounds, and medicines, many of which have mercury as their core element. Its principles restored
the health of those who were ill beyond hope and gave back youth to fading old age." One thing is sure though,
Indian alchemy like every other Indian science is focused on finding Moksha: perfection, immortality, liberation. As
such it focuses its efforts on transmutation of the human body: from mortal to immortal. Many are the traditional
stories of alchemists still alive since time immemorial due to the effects of their experiments.
The texts of Ayurvedic Medicine and Science have aspects similar to alchemy: concepts of cures for all known
diseases, and treatments that focus on anointing the body with oils.
Since alchemy eventually became engrained in the vast field of Indian erudition, influences from other metaphysical
and philosophical doctrines such as Samkhya, Yoga, Vaisheshika and Ayurveda were inevitable. Nonetheless, most
of the Rasayna texts track their origins back to Kaula tantric schools associated to the teachings of the personality of
Matsyendranath.
The Rasayna was understood by very few people at the time. Two famous examples were Nagarjunacharya and
Nityanadhiya. Nagarjunacharya was a Buddhist monk who, in ancient times, ran the great university of Nagarjuna
Sagar. His famous book, Rasaratanakaram, is a famous example of early Indian medicine. In traditional Indian
medicinal terminology "rasa" translates as "mercury" and Nagarjunacharya was said to have developed a method to
convert the mercury into gold. Much of his original writings are lost to us, but his teachings still have strong
influence on traditional Indian medicine (Ayurveda) to this day.
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13
Chinese alchemy
Whereas Western alchemy eventually centered on the transmutation of base metals into
noble ones, Chinese alchemy had a more obvious connection to medicine. The
philosopher's stone of European alchemists can be compared to the Grand Elixir of
Immortality sought by Chinese alchemists. However, in the hermetic view, these two goals
were not unconnected, and the philosopher's stone was often equated with the universal
panacea; therefore, the two traditions may have had more in common than initially appears.
Taoist Alchemists often
Black powder may have been an important invention of Chinese alchemists. Described in
use this alternate version
9th century texts and used in fireworks in China by the 10th century, it was used in
of the Taijitu.
cannons by 1290. From China, the use of gunpowder spread to Japan, the Mongols, the
Arab world, and Europe. Gunpowder was used by the Mongols against the Hungarians in 1241, and in Europe by the
14th century.
Chinese alchemy was closely connected to Taoist forms of traditional Chinese medicine, such as Acupuncture and
Moxibustion, and to martial arts such as Tai Chi Chuan and Kung Fu (although some Tai Chi schools believe that
their art derives from the philosophical or hygienic branches of Taoism, not Alchemical). In fact, in the early Song
Dynasty, followers of this Taoist idea (chiefly the elite and upper class) would ingest mercuric sulfide, which,
though tolerable in low levels, led many to suicide. Thinking that this consequential death would lead to freedom and
access to the Taoist heavens, the ensuing deaths encouraged people to eschew this method of alchemy in favor of
external sources (the aforementioned Tai Chi Chuan, mastering of the Qi, etc.).
Modern alchemy
Due to the complexity and obscurity of alchemical literature, and the eighteenth century disappearance of remaining
alchemical practitioners into the area of chemistry; the general understanding of alchemy in the general public,
modern practitioners, and also many historians of science, have been strongly influenced by several distinct and
radically different interpretations.[90] Hundreds of books including adulterated translations of classical alchemical
literature were published throughout the early nineteenth century.[20] Many of these continue to be reprinted today by
esoteric book publishing houses, along with modern books on spiritual alchemy and poor translations of older
alchemical texts. These are then used as sources by modern authors to support spiritual interpretations. Over half of
the books on alchemy published since 1970 support spiritual interpretations, mostly using previously adulterated
documents to support their conclusions. Many of these books continue to be taken seriously, even appearing in
university bookshelves.[91]
Esoteric interpretations of alchemy remains strong to this day, and continue to influence both the public and
academic perceptions of the history of alchemy. Today, numerous esoteric alchemical groups continue to perpetuate
modern interpretations of alchemy, sometimes merging in concepts from New Age or radical environmentalism
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movements.[92] Rosencrutzians and freemasons have a continued interest in alchemy and its symbolism.
Nuclear transmutation
In 1919, Ernest Rutherford used artificial disintegration to convert nitrogen into oxygen.[95] From then on, this sort
of scientific transmutation is routinely performed in many nuclear physics-related laboratories and facilities, like
particle accelerators, nuclear power stations and nuclear weapons as a by-product of fission and other physical
processes.
The synthesis of noble metals enjoyed brief popularity in the 20th century when physicists were able to convert
platinum atoms into gold atoms via a nuclear reaction. However, the new gold atoms, being unstable isotopes, lasted
for under five seconds before they broke apart. More recently, reports of table-top element transmutationby means
of electrolysis or sonic cavitationwere the pivot of the cold fusion controversy of 1989. None of those claims have
yet been reliably duplicated.
Synthesis of noble metals requires either a nuclear reactor or a particle accelerator. Particle accelerators use huge
amounts of energy, while nuclear reactors produce energy, so only methods utilizing a nuclear reactor are of
economic interest.
Psychology
Alchemical symbolism has been used by psychologists such as Carl Jung who reexamined alchemical symbolism
and theory and presented the inner meaning of alchemical work as a spiritual path.[96] [97] Jung was deeply interested
in the occult since his youth, participating in seances, which he used as the basis for his doctoral dissertation "On the
Psychology and Pathology of So-Called Occult Phenomena."[98] In 1913, Jung had already adopted a "spiritualist
and redemptive interpretation of alchemy", likely reflecting his interest in the occult literature of the nineteenth
century.[99] Jung began writing his views on alchemy from the 1920s and continued until the end of his life. His
interpretation of Chinese alchemical texts in terms of his analytical psychology also served the function of
comparing Eastern and Western alchemical imagery and core concepts and hence its possible inner sources
(archetypes).[100] [101] [102]
Jung saw alchemy as a Western proto-psychology dedicated to the achievement of individuation.[96] [102] In his
interpretation, alchemy was the vessel by which Gnosticism survived its various purges into the Renaissance,[102]
[103]
a concept also followed by others such as Stephan A. Hoeller. In this sense, Jung viewed alchemy as
comparable to a Yoga of the East, and more adequate to the Western mind than Eastern religions and philosophies.
The practice of Alchemy seemed to change the mind and spirit of the Alchemist. Conversely, spontaneous changes
on the mind of Western people undergoing any important stage in individuation seems to produce, on occasion,
imagery known to Alchemy and relevant to the person's situation.[104] Jung did not completely reject the material
experiments of the alchemists, but he massively downplayed it, writing that the transmutation was performed in the
mind of the alchemist. He claimed the material substances and procedures were only a projection of the alchemists'
internal state, while the real substance to be transformed was the mind itself.[105]
14
Alchemy
Marie-Louise von Franz, a disciple of Jung, continued Jung's studies on alchemy and its psychological meaning.
Jung's work exercised a great influence on the mainstream perception of alchemy, his approach becoming a stock
element in many popular texts on the subject to this day.[106] Modern scholars are sometimes critical of the Jungian
approach to alchemy as overly reflective of nineteenth century occultism.[107]
Magnum opus
The Great Work of Alchemy is often described as a series of four stages represented by colors.
Notes
[1] Alchemy at Dictionary.com (http:/ / dictionary. reference. com/ browse/ alchemy).
[2] For a detailed look into the problems of defining alchemy see Stanton J. Linden. Darke Hierogliphicks: Alchemy in English literature from
Chaucer to the Restoration. University Press of Kentucky, 1996. pp. 636
[3] E. J. Holmyard. Alchemy. p.16
[4] Antoine Faivre, Wouter J. Hanegraaff. Western esotericism and the science of religion. 1995. p.96
[5] von Franz, M-L. Alchemical Active Imagination. Shambala. Boston. 1997. ISBN 0-87773-589-1.
[6] N.C. Datta. The Story of Chemistry. p.23
[7] Arthur Greenburg. From alchemy to chemistry in picture and story.
[8] H. Stanley Redgrove. Alchemy Ancient and Modern p.60
[9] Mitch Stokes. Isaac Newton p. 57
[10] Secrets of Nature, Astrology and Alchemy in Modern Europe by William R. Newman, Anthony Grafton, MIT Press, 2006, pp 3978,400
[11] William R Newman & Lawrence M Principe (1998) "The Etymological Origins of an Historiographic Mistake" in Early Science and
Medicine, Vol. 3, No. 1 pp. 3265
[12] Deem, Rich (2005). "The Religious Affiliation of Robert Boyle the father of modern chemistry. From: Famous Scientists Who Believed in
God" (http:/ / www. adherents. com/ people/ pb/ Robert_Boyle. html). adherents.com. . Retrieved 2009-04-17.
[13] More, Louis Trenchard (January 1941). "Boyle as Alchemist". Journal of the History of Ideas (University of Pennsylvania Press) 2 (1):
6176. doi:10.2307/2707281. JSTOR2707281.
[14] Allen G. Debus. Alchemy and early modern chemistry. The Society for the History of Alchemy and Chemistry. p.34.
[15] Raphael Patai. The Jewish Alchemists: A History and Source Book. Princeton University Press. p.4
[16] Thodore Henri de Tschudi. Hermetic Catechism in his L'Etoile Flamboyant ou la Socit des Franc-Maons considere sous tous les
aspects. 1766. (A.E. Waite translation as found in The Hermetic and Alchemical Writings of Paracelsus.)
[17] Raphael Patai. The Jewish Alchemists: A History and Source Book. Princeton University Press. p.3
[18] Daniel Merkur. Gnosis: an esoteric tradition of mystical visions and unions. State University of New York Press. p.75
[19] Alchemy Tried in the Fire by William R. Newman, Lawrence M Principe, p37
[20] Newton and Newtonianism by James E. Force, Sarah Hutton, p211
[21] Secrets of Nature, Astrology and Alchemy in Modern Europe by William R. Newman, Anthony Grafton, MIT Press, 2006, pp 3956
[22] Calian, George (2010). Alkimia Operativa and Alkimia Speculativa. Some Modern Controversies on the Historiography of Alchemy. Annual
of Medieval Studies at CEU.
[23] alchemy (http:/ / oxforddictionaries. com/ view/ entry/ m_en_gb0017630#DWS-M_EN_GB-037342), Oxford Dictionaries
[24] " alchemy (http:/ / oed. com/ search?searchType=dictionary& q=alchemy)". Oxford English Dictionary. Oxford University Press. 2nd ed.
1989. Or see Harper, Douglas. "alchemy" (http:/ / www. etymonline. com/ index. php?term=alchemy). Online Etymology Dictionary. .
Retrieved 2010-04-07..
[25] See, for example, the etymology for in Liddell, Henry George; Robert Scott (1901). A Greek-English Lexicon (Eighth edition,
revised throughout ed.). Oxford: Clarendon Press. ISBN0199102058.
[26] See, for example, both the etymology given in the Oxford English Dictionary and also that for in Liddell, Henry George; Robert
Scott, Henry Stuart Jones (1940). A Greek-English Lexicon (http:/ / www. perseus. tufts. edu/ hopper/ morph?l=xumeia& la=greek#lexicon)
(A new edition, revised and augmented throughout ed.). Oxford: Clarendon Press. ISBN0199102058. .
[27] The original source for this analysis is the article on pp.8185 of Mahn, Carl August Friedrich (1855). Etymologische untersuchungen auf
dem gebiete der romanischen sprachen (http:/ / books. google. com/ ?id=-BMLAAAAQAAJ). F. Duemmler. .
[28] The article by David Bain, entitled " , an unnoticed Greek name for Egypt: New evidence for the origins and etymology of
alchemy?" expresses the current debate. The world of ancient magic (http:/ / www. norwinst. gr/ papers. html). Bergen: The Norwegian
15
Alchemy
Institute at Athens. 1999. .
[29] New Scientist, December 2431, 1987
[30] Garfinkel, Harold (1986). Ethnomethodological Studies of Work. Routledge &Kegan Paul. pp.127. ISBN0415119650.
[31] Yves Bonnefoy. Roman and European Mythologies. University of Chicago Press, 1992. pp. 211213
[32] Clement, Stromata, vi. 4.
[33] Stanton J. Linden. Darke Hierogliphicks: Alchemy in English literature from Chaucer to the Restoration. University Press of Kentucky,
1996. p.12
[34] Partington, James Riddick (1989). A Short History of Chemistry. New York: Dover Publications. pp.20. ISBN0486659771.
[35] The Alchemy Reader: From Hermes Trismegistus to Isaac Newton, Stanton J. Linden, Cambridge University Press, 2003, p46
[36] A History of Chemistry, Bensaude-Vincent, Isabelle Stengers, Harvard University Press, 1996, p13
[37] Stanton J. Linden. Darke Hierogliphicks: Alchemy in English literature from Chaucer to the Restoration. University Press of Kentucky,
1996. p.14
[38] A History of Chemistry, Bensaude-Vincent, Isabelle Stengers, Harvard University Press, 1996, p13
[39] Lindsay, Jack (1970). The Origins of Alchemy in Graeco-Roman Egypt. London: Muller. p.16. ISBN0-389-01006-5.
[40] Hitchcock, Ethan Allen (1857). Remarks Upon Alchemy and the Alchemists. Boston: Crosby, Nichols. p.66. ISBN0405079559.
[41] Fanning, Philip Ashley. Isaac Newton and the Transmutation of Alchemy: An Alternative View of the Scientific Revolution. 2009. p.6
[42] F. Sherwood Taylor. Alchemists, Founders of Modern Chemistry. p.26.
[43] Allen G. Debus. Alchemy and early modern chemistry: papers from Ambix. p. 36
[44] Glen Warren Bowersock, Peter Robert Lamont Brown, Oleg Grabar. Late antiquity: a guide to the postclassical world. p. 284285
[45] Burckhardt, Titus (1967). Alchemy: Science of the Cosmos, Science of the Soul. Trans. William Stoddart. Baltimore: Penguin. p.46.
ISBN0906540968.
[46] Kraus, Paul, Jbir ibn Hayyn, Contribution l'histoire des ides scientifiques dans l'Islam. I. Le corpus des crits jbiriens. II. Jbir et la
science grecque,. Cairo (19421943). Repr. By Fuat Sezgin, (Natural Sciences in Islam. 6768), Frankfurt. 2002: (cf. Ahmad Y Hassan. "A
Critical Reassessment of the Geber Problem: Part Three" (http:/ / www. history-science-technology. com/ Geber/ Geber 3. htm). . Retrieved
2008-08-09.)
[47] Derewenda, Zygmunt S. (2007). "On wine, chirality and crystallography". Acta Crystallographica Section A: Foundations of
Crystallography 64: 246258 [247]. doi:10.1107/S0108767307054293. PMID18156689.
[48] Holmyard, E. J. (1931). Makers of Chemistry (http:/ / www. archive. org/ details/ makersofchemistr029725mbp). Oxford: Clarendon Press.
p.60. .
[49] Burckhardt, Titus (1967). Alchemy: Science of the Cosmos, Science of the Soul. Trans. William Stoddart. Baltimore: Penguin. p.29.
ISBN0906540968.
[50] Strathern, Paul. (2000), Mendeleyevs Dream the Quest for the Elements, New York: Berkley Books
[51] Moran, Bruce T. (2005). Distilling knowledge: alchemy, chemistry, and the scientific revolution. Harvard University Press. p.146.
ISBN0674014952. "a corpuscularian tradition in alchemy stemming from the speculations of the medieval author Geber (Jabir ibn Hayyan)"
[52] Research Committee of Strasburg University, Imam Jafar Ibn Muhammad As-Sadiq A.S. The Great Muslim Scientist and Philosopher,
translated by Kaukab Ali Mirza, 2000. Willowdale Ont. ISBN 0969949014.
[53] Felix Klein-Frank (2001), "Al-Kindi", in Oliver Leaman & Hossein Nasr, History of Islamic Philosophy, p. 174. London: Routledge.
[54] Marmura Michael E. (1965). "An Introduction to Islamic Cosmological Doctrines: Conceptions of Nature and Methods Used for Its Study
by the Ikhwan Al-Safa'an, Al-Biruni, and Ibn Sina by Seyyed Hossein Nasr". Speculum 40 (4): 7446. doi:10.2307/2851429.
[55] Robert Briffault (1938). The Making of Humanity, p. 196197.
[56] E.J. Holmyard. Alchemy. 1990. p.105-108
[57] E.J. Holmyard. Alchemy. 1990. p.110
[58] Hollister, C. Warren (1990). Medieval Europe: A Short History (6th ed.). Blacklick, Ohio: McGrawHill College. pp.294f.
ISBN0-07-557141-2.
[59] John Read. From Alchemy to Chemistry. 1995 p.90
[60] James A. Weisheipl. Albertus Magnus and the Sciences: Commemorative Essays. PIMS. 1980. p.187-202
[61] Edmund Brehm. "Roger Bacons Place in the History of Alchemy." Ambix. Vol. 23, Part I, March 1976.
[62] E.J. Holmyard. Alchemy. Courier Dover Publications, 1990. p.120-121
[63] E.J. Holmyard Alchemy. Dover. 1990. p. 134-141.
[64] Burckhardt, Titus (1967). Alchemy: Science of the Cosmos, Science of the Soul. Trans. William Stoddart. Baltimore: Penguin. p.149.
ISBN0906540968.
[65] Tara E. Nummedal. Alchemy and Authority in the Holy Roman Empire. University of Chicago Press, 2007. p. 49
[66] John Hines, II, R. F. Yeager. John Gower, Trilingual Poet: Language, Translation, and Tradition. Boydell & Brewer. 2010. p.170
[67] Leah DeVun. From Prophecy, Alchemy, and the End of Time: John of Rupescissa in the late middle ages. Columbia University Press, 2009.
p. 104
[68] Burckhardt, Titus (1967). Alchemy: Science of the Cosmos, Science of the Soul. Trans. William Stoddart. Baltimore: Penguin. pp.170181.
ISBN0906540968.
[69] Stanton J. Linden. The Alchemy Reader: From Hermes Trismegistus to Isaac Newton. Cambridge University Press, 2003. p.123
[70] Edwardes, Michael (1977). The Dark Side of History. New York: Stein and Day. pp.5659. ISBN0552114634.
16
Alchemy
17
[71] Wilson, Colin (1971). The Occult: A History. New York: Random House. pp.2329. ISBN0-394-46555-5.
[72] Edwardes, Michael (1977). The Dark Side of History. New York: Stein and Day. p.47. ISBN0552114634.
[73] Debus, Allen G. and Multhauf, Robert P. (1966). Alchemy and Chemistry in the Seventeenth Century. Los Angeles: William Andrews Clark
Memorial Library, University of California.. pp.612.
[74] Davis, Erik. "The Gods of the Funny Books: An Interview with Neil Gaiman and Rachel Pollack" (http:/ / www. techgnosis. com/ gaiman.
html). Gnosis (magazine). Techgnosis (reprint from Summer 1994 issue). . Retrieved 2007-02-04.
[75] Accounts of the Lord High Treasurer of Scotland, vol. iii, (1901), 99, 202, 206, 209, 330, 340, 341, 353, 355, 365, 379, 382, 389, 409.
[76] Pilkington, Roger (1959). Robert Boyle: Father of Chemistry. London: John Murray. p.11.
On the Edge of the Future by Jeffrey John Kripal, Glenn W. Shuck, p27
Secrets of Nature, Astrology and Alchemy in Modern Europe by William R. Newman, Anthony Grafton, MIT Press, 2006, p387
[84] Secrets of Nature, Astrology and Alchemy in Modern Europe by William R. Newman, Anthony Grafton, MIT Press, 2006, p388
[85] Secrets of Nature, Astrology and Alchemy in Modern Europe by William R. Newman, Anthony Grafton, MIT Press, 2006, p391
[86] Secrets of Nature, Astrology and Alchemy in Modern Europe by William R. Newman, Anthony Grafton, MIT Press, 2006, p143.
[87] Multhauf, Robert P. & Gilbert, Robert Andrew (2008). Alchemy. Encyclopdia Britannica (2008).
[88] Antoine Faivre, Wouter J. Hanegraaff. Western esotericism and the science of religion. 1995. p.viiixvi
[89] See Exeter Centre for the Study of Esotericism website (http:/ / centres. exeter. ac. uk/ exeseso/ )
[90] Secrets of Nature, Astrology and Alchemy in Modern Europe by William R. Newman, Anthony Grafton, MIT Press, 2006, p385
[91] Secrets of Nature, Astrology and Alchemy in Modern Europe by William R. Newman, Anthony Grafton, MIT Press, 2006, pp 3956
[92] Secrets of Nature, Astrology and Alchemy in Modern Europe by William R. Newman, Anthony Grafton, MIT Press, 2006, p396
[93] Junius, Manfred M; The Practical Handbook of Plant Alchemy: An Herbalist's Guide to Preparing Medicinal Essences, Tinctures, and
Elixirs; Healing Arts Press 1985
[94] Joscelyn Godwin. The Golden Thread: The Ageless Wisdom of the Western Mystery Traditions. Quest Books, 2007. p.120
[95] [ |Amsco School Publications (http:/ / worthyisthelamb. info/ amsco/ newtitles. html)]. "Reviewing Physics: The Physical Setting" (http:/ /
www. stmary. ws/ physics/ amsco_review_and_glencoe/ chapter05. pdf). Amsco School Publications. . ""The first artificial transmutation of
one element to another was performed by Rutherford in 1919. Rutherford bombarded nitrogen with energetic alpha particles that were moving
fast enough to overcome the electric repulsion between themselves and the target nuclei. The alpha particles collided with, and were absorbed
by, the nitrogen nuclei, and protons were ejected. In the process oxygen and hydrogen nuclei were created."
[96] Jung, C. G. (1944). Psychology and Alchemy (2nd ed. 1968 Collected Works Vol. 12 ISBN 0-691-01831-6). London: Routledge.
[97] Jung, C. G., & Hinkle, B. M. (1912). Psychology of the Unconscious : a study of the transformations and symbolisms of the libido, a
contribution to the history of the evolution of thought. London: Kegan Paul Trench Trubner. (revised in 1952 as Symbols of Transformation,
Collected Works Vol.5 ISBN 0-691-01815-4).
[98] The Jung Cult, by Ricard Noll, Princeton University Press, 1994, p144
[99] Noll. Aryan Christ. p171
[100] C.-G. Jung Preface to Richard Wilhelm's translation of the I Ching.
[101] C.-G. Jung Preface to the translation of The Secret of The Golden Flower.
[102] Polly Young-Eisendrath, Terence Dawson. The Cambridge companion to Jung. Cambridge University Press. 1997. p.33
[103] Jung, C. G., & Jaffe A. (1962). Memories, Dreams, Reflections. London: Collins. This is Jung's autobiography, recorded and edited by
Aniela Jaffe, ISBN 0-679-72395-1.
[104] Jung, C. G.Psychology and Alchemy; Symbols of Transformation.
[105] Redemption in Alchemy, by Carl Jung, p210
[106] Secrets of Nature, Astrology and Alchemy in Modern Europe by William R. Newman, Anthony Grafton, MIT Press, 2006, p401
Secrets of Nature, Astrology and Alchemy in Modern Europe by William R. Newman, Anthony Grafton, MIT Press, 2006, p418
Alchemy Tried in the Fire, by William R. Newman, Lawrence M. Principe, p37
On the Edge of the Future, by Jeffrey John Kripal, Glenn W. Shuck, p27
[108] Joseph Needham. Science & Civilisation in China: Chemistry and chemical technology. Spagyrical discovery and invention : magisteries
of gold and immortality. Cambridge. 1974. p.23
Alchemy
References
Calian, George (2010). Alkimia Operativa and Alkimia Speculativa. Some Modern Controversies on the
Historiography of Alchemy (http://www.archive.org/stream/AlkimiaOperativaAndAlkimiaSpeculativa.
SomeModernControversiesOnThe/FlorinGeorgeCalian-AlkimiaOperativaAndAlkimiaSpeculativa.
SomeModernControversiesOnTheHistoriographyOfAlchemy#page/n0/mode/2up). Annual of Medieval Studies
at CEU.
Eliade, Mircea (1978). The Forge and the Crucible (http://books.google.com/books?id=SQDJ1aCtMV8C&
printsec=frontcover#v=onepage&q&f=false). Chicago: University of Chicago Press.
Halleux, Robert (1979). Les textes alchimiques. Brepols Publishers.
Holmyard, Eric John (1957). Alchemy (http://books.google.com/books?id=7Bt-kwKRUzUC&lpg=PP1&
dq=alchemy&pg=PP1&hl=en#v=onepage&q&f=false). Courier Dover Publications.
Janacek, Bruce, Alchemical Belief: Occultism in the Religious Culture of Early Modern England (University Park
(PA), Pennsylvania State UP, 2011) (Magic in History).
Linden, Stanton J. (2003). The Alchemy Reader: from Hermes Trismegistus to Isaac Newton (http://books.
google.com/books?id=isJY9jWdru0C&lpg=PP1&dq=alchemy&pg=PP1#v=onepage&q&f=false).
Cambridge University Press.
Newman, William R.; Principe, Lawrence M. (2002). Alchemy Tried in the Fire (http://books.google.com/
books?id=eQERmMdykZEC&lpg=PP1&dq=alchemy&pg=PP1#v=onepage&q&f=false). The University of
Chicago Press..
von Franz, Marie Louise (1980). Alchemy: An Introduction to the Symbolism and the Psychology (http://books.
google.com/books?id=wOVUUMirSnEC&lpg=PP1&dq=alchemy&pg=PP1#v=onepage&q&f=false). Inner
City Books.
External links
Alchemy (http://www.bbc.co.uk/programmes/p003k9bn) on In Our Time at the BBC. ( listen now (http://
www.bbc.co.uk/iplayer/console/p003k9bn/In_Our_Time_Alchemy))
Etymology of "alchemy" (http://www.balashon.com/2009/03/alchemy.html)
Hidden Symbolism of Alchemy and the Occult Arts (http://www.gutenberg.org/etext/27755) Full-length book
by Herbert Silberer
Alchemy images (http://www.alchemywebsite.com/emb_apparatus.html)
Dictionary of the History of Ideas: (http://xtf.lib.virginia.edu/xtf/view?docId=DicHist/uvaBook/tei/
DicHist1.xml;chunk.id=dv1-04) Alchemy
Antiquity, Vol. 77 (2003) "A 16th century lab in a 21st century lab". (http://antiquity.ac.uk/ProjGall/martinon/
index.html) Origins of modern chemistry in alchemy
The Story of Alchemy and the Beginnings of Chemistry (http://www.gutenberg.org/etext/14218), Muir, M. M.
Pattison (1913)
"Transforming the Alchemists" (http://www.nytimes.com/2006/08/01/science/01alch.
html?ex=1312084800&en=4445e5f8f9c7b3c0&ei=5090&partner=rssuserland&emc=rss), New York Times,
August 1, 2006. Recent historical scholarship on alchemy.
Electronic library (http://www.revistaazogue.com/biblio.htm#N_3_) with hundreds of alchemical books (15th
and 20th century) and 160 original manuscripts.
SHAC: Society for the History of Alchemy and Chemistry (http://www.ambix.org/)
Book of Secrets: Alchemy and the European Imagination, 1500-2000 (http://beinecke.library.yale.edu/
digitallibrary/alchemy.html) A digital exhibition from the Beinecke Rare Book and Manuscript Library at Yale
University (http://www.library.yale.edu/beinecke/)
18
Chemistry
19
Chemistry
Chemistry is the science of matter, especially its chemical reactions,
but also its composition, structure and properties.[1] [2] Chemistry is
concerned with atoms and their interactions with other atoms, and
particularly with the properties of chemical bonds.
Chemistry is sometimes called "the central science" because it
connects physics with other natural sciences such as geology and
biology.[3] [4] Chemistry is a branch of physical science but distinct
from physics.[5]
The etymology of the word chemistry has been much disputed.[6] The
genesis of chemistry can be traced to certain practices, known as
alchemy, which had been practiced for several millennia in various
parts of the world, particularly the Middle East.[7]
Theory
Traditional chemistry starts with the study of elementary particles,
atoms, molecules,[8] substances, metals, crystals and other aggregates
of matter. in solid, liquid, and gas states, whether in isolation or
combination. The interactions, reactions and transformations that are
studied in chemistry are a result of interaction either between different
chemical substances or between matter and energy. Such behaviors are
studied in a chemistry laboratory using various forms of laboratory
glassware.
During chemical reactions, bonds between atoms
break and form, resulting in different substances
with different properties. In a blast furnace, iron
oxide, a compound, reacts with carbon monoxide
to form iron, one of the chemical elements, and
carbon dioxide.
Chemistry
20
History
Ancient Egyptians pioneered the art of synthetic "wet" chemistry up to 4,000 years ago.[11] By 1000 BC ancient
civilizations were using technologies that formed the basis of the various branches of chemistry such as; extracting
metal from their ores, making pottery and glazes, fermenting beer and wine, making pigments for cosmetics and
painting, extracting chemicals from plants for medicine and perfume, making cheese, dying cloth, tanning leather,
rendering fat into soap, making glass, and making alloys like bronze.
The genesis of chemistry can be traced to the widely observed phenomenon of
burning that led to metallurgythe art and science of processing ores to get
metals (e.g. metallurgy in ancient India). The greed for gold led to the discovery
of the process for its purification, even though the underlying principles were not
well understoodit was thought to be a transformation rather than purification.
Many scholars in those days thought it reasonable to believe that there exist
means for transforming cheaper (base) metals into gold. This gave way to
alchemy and the search for the Philosopher's Stone which was believed to bring
about such a transformation by mere touch.[12]
Greek atomism dates back to 440 BC, as what might be indicated by the book De
Rerum Natura (The Nature of Things)[13] written by the Roman Lucretius in 50
BC.[14] Much of the early development of purification methods is described by
Pliny the Elder in his Naturalis Historia.
The most influential Muslim chemists were Jbir ibn Hayyn (Geber, d. 815), al-Kindi (d. 873), al-Razi (d. 925),
al-Biruni (d. 1048) and Alhazen (d. 1039).[18] The works of Jbir became more widely known in Europe through
Latin translations by a pseudo-Geber in 14th century Spain, who also wrote some of his own books under the pen
Chemistry
name "Geber". The contribution of Indian alchemists and metallurgists in the development of chemistry was also
quite significant.[19]
The emergence of chemistry in Europe was primarily due to the recurrent incidence of the plague and blights there
during the so called Dark Ages. This gave rise to a need for medicines. It was thought that there exists a universal
medicine called the Elixir of Life that can cure all diseases, but like the Philosopher's Stone, it was never found.
For some practitioners, alchemy was an intellectual pursuit, over time,
they got better at it. Paracelsus (14931541), 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. Similarly, the influences of
philosophers such as Sir Francis Bacon (15611626) and Ren
Descartes (15961650), who demanded more rigor in mathematics and
in removing bias from scientific observations, led to a scientific
revolution. In chemistry, this began with Robert Boyle (16271691),
who came up with an equation known as Boyle's Law about the
characteristics of gaseous state.[21]
Chemistry indeed came of age when Antoine Lavoisier (17431794),
developed the theory of Conservation of mass in 1783; and the
development of the Atomic Theory by John Dalton around 1800. The
Law of Conservation of Mass resulted in the reformulation of
chemistry based on this law and the oxygen theory of combustion,
Antoine-Laurent de Lavoisier is considered the
which was largely based on the work of Lavoisier. Lavoisier's
[20]
"Father of Modern Chemistry".
fundamental contributions to chemistry were a result of a conscious
effort to fit all experiments into the framework of a single theory. He
established the consistent use of the chemical balance, used oxygen to overthrow the phlogiston theory, and
developed a new system of chemical nomenclature and made contribution to the modern metric system. Lavoisier
also worked to translate the archaic and technical language of chemistry into something that could be easily
understood by the largely uneducated masses, leading to an increased public interest in chemistry. All these advances
in chemistry led to what is usually called the chemical revolution. The contributions of Lavoisier led to what is now
called modern chemistrythe chemistry that is studied in educational institutions all over the world. It is because of
these and other contributions that Antoine Lavoisier is often celebrated as the "Father of Modern Chemistry".[22] The
later discovery of Friedrich Whler that many natural substances, organic compounds, can indeed be synthesized in a
chemistry laboratory also helped the modern chemistry to mature from its infancy.[23]
The discovery of the chemical elements has a long history from the days of alchemy and culminating in the
discovery of the periodic table of the chemical elements by Dmitri Mendeleev (18341907)[24] and later discoveries
of some synthetic elements.
Etymology
The word chemistry comes from the word alchemy, an earlier set of practices that encompassed elements of
chemistry, metallurgy, philosophy, astrology, astronomy, mysticism and medicine; it is commonly thought of as the
quest to turn lead or another common starting material into gold.[25] The word alchemy in turn is derived from the
Arabic word al-km (), meaning alchemy. The Arabic term is borrowed from the Greek or .[26]
[27]
This may have Egyptian origins. Many believe that al-km is derived from , which is in turn derived from
the word Chemi or Kimi, which is the ancient name of Egypt in Egyptian.[26] Alternately, al-km may be derived
from , meaning "cast together".[28]
21
Chemistry
An alchemist was called a 'chemist' in popular speech, and later the suffix "-ry" was added to this to describe the art
of the chemist as "chemistry".
Definitions
In retrospect, the definition of chemistry has changed over time, as new discoveries and theories add to the
functionality of the science. Shown below are some of the standard definitions used by various noted chemists:
Alchemy (330) the study of the composition of waters, movement, growth, embodying, disembodying, drawing
the spirits from bodies and bonding the spirits within bodies (Zosimos).[29]
Chymistry (1661) the subject of the material principles of mixed bodies (Boyle).[30]
Chymistry (1663) a scientific art, by which one learns to dissolve bodies, and draw from them the different
substances on their composition, and how to unite them again, and exalt them to a higher perfection (Glaser).[31]
Chemistry (1730) the art of resolving mixed, compound, or aggregate bodies into their principles; and of
composing such bodies from those principles (Stahl).[32]
Chemistry (1837) the science concerned with the laws and effects of molecular forces (Dumas).[33]
Chemistry (1947) the science of substances: their structure, their properties, and the reactions that change them
into other substances (Pauling).[34]
Chemistry (1998) the study of matter and the changes it undergoes (Chang).[35]
Basic concepts
Several concepts are essential for the study of chemistry; some of them are:[36]
Atom
An atom is the basic unit of chemistry. It consists of a positively charged core (the atomic nucleus) which contains
protons and neutrons, and which maintains a number of electrons to balance the positive charge in the nucleus. The
atom is also the smallest entity that can be envisaged to retain the chemical properties of the element, such as
electronegativity, ionization potential, preferred oxidation state(s), coordination number, and preferred types of
bonds to form (e.g., metallic, ionic, covalent).
Element
The concept of chemical element is related to that of chemical substance. A chemical element is specifically a
substance which is composed of a single type of atom. A chemical element is characterized by a particular number of
protons in the nuclei of its atoms. This number is known as the atomic number of the element. For example, all
atoms with 6 protons in their nuclei are atoms of the chemical element carbon, and all atoms with 92 protons in their
nuclei are atoms of the element uranium. Although all the nuclei of all atoms belonging to one element will have the
same number of protons, they may not necessarily have the same number of neutrons; such atoms are termed
isotopes. In fact several isotopes of an element may exist. Ninetyfour different chemical elements or types of atoms
based on the number of protons are observed on earth naturally, having at least one isotope that is stable or has a
very long half-life. A further 18 elements have been recognised by IUPAC after they have been made in the
laboratory.
The standard presentation of the chemical elements is in the periodic table, which orders elements by atomic number
and groups them by electron configuration. Due to its arrangement, groups, or columns, and periods, or rows, of
elements in the table either share several chemical properties, or follow a certain trend in characteristics such as
atomic radius, electronegativity, etc. Lists of the elements by name, by symbol, and by atomic number are also
available.
22
Chemistry
Compound
A compound is a substance with a particular ratio of atoms of particular chemical elements which determines its
composition, and a particular organization which determines chemical properties. For example, water is a compound
containing hydrogen and oxygen in the ratio of two to one, with the oxygen atom between the two hydrogen atoms,
and an angle of 104.5 between them. Compounds are formed and interconverted by chemical reactions.
Substance
A chemical substance is a kind of matter with a definite composition and set of properties.[37] Strictly speaking, a
mixture of compounds, elements or compounds and elements is not a chemical substance, but it may be called a
chemical. Most of the substances we encounter in our daily life are some kind of mixture; for example: air, alloys,
biomass, etc.
Nomenclature of substances is a critical part of the language of chemistry. Generally it refers to a system for naming
chemical compounds. Earlier in the history of chemistry substances were given name by their discoverer, which
often led to some confusion and difficulty. However, today the IUPAC system of chemical nomenclature allows
chemists to specify by name specific compounds amongst the vast variety of possible chemicals. The standard
nomenclature of chemical substances is set by the International Union of Pure and Applied Chemistry (IUPAC).
There are well-defined systems in place for naming chemical species. Organic compounds are named according to
the organic nomenclature system.[38] Inorganic compounds are named according to the inorganic nomenclature
system.[39] In addition the Chemical Abstracts Service has devised a method to index chemical substance. In this
scheme each chemical substance is identifiable by a number known as CAS registry number.
Molecule
A molecule is the smallest indivisible portion of a pure chemical substance that has its unique set of chemical
properties, that is, its potential to undergo a certain set of chemical reactions with other substances. However, this
definition only works well for substances that are composed of molecules, which is not true of many substances (see
below). Molecules are typically a set of atoms bound together by covalent bonds, such that the structure is
electrically neutral and all valence electrons are paired with other electrons either in bonds or in lone pairs. Thus,
molecules exist as electrically neutral units, unlike ions. When this rule is broken, giving the "molecule" a charge,
the result is sometimes named a molecular ion or a polyatomic ion. However, the discrete and separate nature of the
molecular concept usually requires that molecular ions be present only in well-separated form, such as a directed
beam in a vacuum in a mass spectrograph. Charged polyatomic collections residing in solids (for example, common
sulfate or nitrate ions) are generally not considered "molecules" in chemistry.
23
Chemistry
24
Chemistry
Phase
In addition to the specific chemical properties that distinguish different chemical classifications chemicals can exist
in several phases. For the most part, the chemical classifications are independent of these bulk phase classifications;
however, some more exotic phases are incompatible with certain chemical properties. A phase is a set of states of a
chemical system that have similar bulk structural properties, over a range of conditions, such as pressure or
temperature. Physical properties, such as density and refractive index tend to fall within values characteristic of the
phase. The phase of matter is defined by the phase transition, which is when energy put into or taken out of the
system goes into rearranging the structure of the system, instead of changing the bulk conditions.
Sometimes the distinction between phases can be continuous instead of having a discrete boundary, in this case the
matter is considered to be in a supercritical state. When three states meet based on the conditions, it is known as a
triple point and since this is invariant, it is a convenient way to define a set of conditions.
The most familiar examples of phases are solids, liquids, and gases. Many substances exhibit multiple solid phases.
For example, there are three phases of solid iron (alpha, gamma, and delta) that vary based on temperature and
pressure. A principal difference between solid phases is the crystal structure, or arrangement, of the atoms. Another
phase commonly encountered in the study of chemistry is the aqueous phase, which is the state of substances
dissolved in aqueous solution (that is, in water). Less familiar phases include plasmas, Bose-Einstein condensates
and fermionic condensates and the paramagnetic and ferromagnetic phases of magnetic materials. While most
familiar phases deal with three-dimensional systems, it is also possible to define analogs in two-dimensional
systems, which has received attention for its relevance to systems in biology.
25
Chemistry
Redox
It is a concept related to the ability of atoms of various substances to lose or gain electrons. Substances that have the
ability to oxidize other substances are said to be oxidative and are known as oxidizing agents, oxidants or oxidizers.
An oxidant removes electrons from another substance. Similarly, substances that have the ability to reduce other
substances are said to be reductive and are known as reducing agents, reductants, or reducers. A reductant transfers
electrons to another substance, and is thus oxidized itself. And because it "donates" electrons it is also called an
electron donor. Oxidation and reduction properly refer to a change in oxidation numberthe actual transfer of
electrons may never occur. Thus, oxidation is better defined as an increase in oxidation number, and reduction as a
decrease in oxidation number.
Bonding
Atoms sticking together in molecules or crystals are said to be bonded
with one another. A chemical bond may be visualized as the multipole
balance between the positive charges in the nuclei and the negative
charges oscillating about them.[43] More than simple attraction and
repulsion, the energies and distributions characterize the availability of
an electron to bond to another atom.
A chemical bond can be a covalent bond, an ionic bond, a hydrogen
bond or just because of Van der Waals force. Each of these kind of
Electron atomic and molecular orbitals
bond is ascribed to some potential. These potentials create the
interactions which hold atoms together in molecules or crystals. In many simple compounds, Valence Bond Theory,
the Valence Shell Electron Pair Repulsion model (VSEPR), and the concept of oxidation number can be used to
explain molecular structure and composition. Similarly, theories from classical physics can be used to predict many
ionic structures. With more complicated compounds, such as metal complexes, valence bond theory is less
applicable and alternative approaches, such as the molecular orbital theory, are generally used. See diagram on
electronic orbitals.
Reaction
When a chemical substance is transformed as a result of its interaction with another or energy, a chemical reaction is
said to have occurred. Chemical reaction is therefore a concept related to the 'reaction' of a substance when it comes
in close contact with another, whether as a mixture or a solution; exposure to some form of energy, or both. It results
in some energy exchange between the constituents of the reaction as well with the system environment which may
be a designed vessels which are often laboratory glassware. Chemical reactions can result in the formation or
dissociation of molecules, that is, molecules breaking apart to form two or more smaller molecules, or rearrangement
of atoms within or across molecules. Chemical reactions usually involve the making or breaking of chemical bonds.
Oxidation, reduction, dissociation, acid-base neutralization and molecular rearrangement are some of the commonly
used kinds of chemical reactions.
A chemical reaction can be symbolically depicted through a chemical equation. While in a non-nuclear chemical
reaction the number and kind of atoms on both sides of the equation are equal, for a nuclear reaction this holds true
only for the nuclear particles viz. protons and neutrons.[44]
The sequence of steps in which the reorganization of chemical bonds may be taking place in the course of a chemical
reaction is called its mechanism. A chemical reaction can be envisioned to take place in a number of steps, each of
which may have a different speed. Many reaction intermediates with variable stability can thus be envisaged during
the course of a reaction. Reaction mechanisms are proposed to explain the kinetics and the relative product mix of a
reaction. Many physical chemists specialize in exploring and proposing the mechanisms of various chemical
26
Chemistry
reactions. Several empirical rules, like the Woodward-Hoffmann rules often come handy while proposing a
mechanism for a chemical reaction.
According to the IUPAC gold book a chemical reaction is a process that results in the interconversion of chemical
species".[45] Accordingly, a chemical reaction may be an elementary reaction or a stepwise reaction. An additional
caveat is made, in that this definition includes cases where the interconversion of conformers is experimentally
observable. Such detectable chemical reactions normally involve sets of molecular entities as indicated by this
definition, but it is often conceptually convenient to use the term also for changes involving single molecular entities
(i.e. 'microscopic chemical events').
Equilibrium
Although the concept of equilibrium is widely used across sciences, in the context of chemistry, it arises whenever a
number of different states of the chemical composition are possible. For example, in a mixture of several chemical
compounds that can react with one another, or when a substance can be present in more than one kind of phase. A
system of chemical substances at equilibrium even though having an unchanging composition is most often not
static; molecules of the substances continue to react with one another thus giving rise to a dynamic equilibrium. Thus
the concept describes the state in which the parameters such as chemical composition remain unchanged over time.
Chemicals present in biological systems are invariably not at equilibrium; rather they are far from equilibrium.
Energy
In the context of chemistry, energy is an attribute of a substance as a consequence of its atomic, molecular or
aggregate structure. Since a chemical transformation is accompanied by a change in one or more of these kinds of
structure, it is invariably accompanied by an increase or decrease of energy of the substances involved. Some energy
is transferred between the surroundings and the reactants of the reaction in the form of heat or light; thus the
products of a reaction may have more or less energy than the reactants. A reaction is said to be exergonic if the final
state is lower on the energy scale than the initial state; in the case of endergonic reactions the situation is the reverse.
A reaction is said to be exothermic if the reaction releases heat to the surroundings; in the case of endothermic
reactions, the reaction absorbs heat from the surroundings.
Chemical reactions are invariably not possible unless the reactants surmount an energy barrier known as the
activation energy. The speed of a chemical reaction (at given temperature T) is related to the activation energy E, by
the Boltzmann's population factor
- that is the probability of molecule to have energy greater than or equal
to E at the given temperature T. This exponential dependence of a reaction rate on temperature is known as the
Arrhenius equation. The activation energy necessary for a chemical reaction can be in the form of heat, light,
electricity or mechanical force in the form of ultrasound.[46]
A related concept free energy, which also incorporates entropy considerations, is a very useful means for predicting
the feasibility of a reaction and determining the state of equilibrium of a chemical reaction, in chemical
thermodynamics. A reaction is feasible only if the total change in the Gibbs free energy is negative,
; if it
is equal to zero the chemical reaction is said to be at equilibrium.
There exist only limited possible states of energy for electrons, atoms and molecules. These are determined by the
rules of quantum mechanics, which require quantization of energy of a bound system. The atoms/molecules in a
higher energy state are said to be excited. The molecules/atoms of substance in an excited energy state are often
much more reactive; that is, more amenable to chemical reactions.
The phase of a substance is invariably determined by its energy and the energy of its surroundings. When the
intermolecular forces of a substance are such that the energy of the surroundings is not sufficient to overcome them,
it occurs in a more ordered phase like liquid or solid as is the case with water (H2O); a liquid at room temperature
because its molecules are bound by hydrogen bonds.[47] Whereas hydrogen sulfide (H2S) is a gas at room
temperature and standard pressure, as its molecules are bound by weaker dipole-dipole interactions.
27
Chemistry
28
The transfer of energy from one chemical substance to another depends on the size of energy quanta emitted from
one substance. However, heat energy is often transferred more easily from almost any substance to another because
the phonons responsible for vibrational and rotational energy levels in a substance have much less energy than
photons invoked for the electronic energy transfer. Thus, because vibrational and rotational energy levels are more
closely spaced than electronic energy levels, heat is more easily transferred between substances relative to light or
other forms of electronic energy. For example, ultraviolet electromagnetic radiation is not transferred with as much
efficacy from one substance to another as thermal or electrical energy.
The existence of characteristic energy levels for different chemical substances is useful for their identification by the
analysis of spectral lines. Different kinds of spectra are often used in chemical spectroscopy, e.g. IR, microwave,
NMR, ESR, etc. Spectroscopy is also used to identify the composition of remote objects - like stars and distant
galaxies - by analyzing their radiation spectra.
The term chemical energy is often used to indicate the potential of a chemical substance to undergo a transformation
through a chemical reaction or to transform other chemical substances.
Chemical laws
Chemical reactions are governed by certain laws, which have become fundamental concepts in chemistry. Some of
them are:
Avogadro's law
Beer-Lambert law
Boyle's law (1662, relating pressure and volume)
Charles's law (1787, relating volume and temperature)
Fick's law of diffusion
Gay-Lussac's law (1809, relating pressure and temperature)
Le Chatelier's Principle
Henry's law
Hess's Law
Law of conservation of energy leads to the important concepts of equilibrium, thermodynamics, and kinetics.
Law of conservation of mass continues to be conserved in isolated systems, even in modern physics. However,
special relativity shows that due to mass-energy equivalence, whenever non-material "energy" (heat, light, kinetic
energy) is removed from a non-isolated system, some mass will be lost with it. High energy loses result in loss of
weighable amounts of mass, an important topic in nuclear chemistry.
Law of definite composition, although in many systems (notably biomacromolecules and minerals) the ratios tend
to require large numbers, and are frequently represented as a fraction.
Law of multiple proportions
Raoult's Law
Chemistry
Subdisciplines
Chemistry is typically divided into several major sub-disciplines. There are also several main cross-disciplinary and
more specialized fields of chemistry.[48]
Analytical chemistry is the analysis of material samples to gain an understanding of their chemical composition
and structure. Analytical chemistry incorporates standardized experimental methods in chemistry. These methods
may be used in all subdisciplines of chemistry, excluding purely theoretical chemistry.
Biochemistry is the study of the chemicals, chemical reactions and chemical interactions that take place in living
organisms. Biochemistry and organic chemistry are closely related, as in medicinal chemistry or neurochemistry.
Biochemistry is also associated with molecular biology and genetics.
Inorganic chemistry is the study of the properties and reactions of inorganic compounds. The distinction between
organic and inorganic disciplines is not absolute and there is much overlap, most importantly in the sub-discipline
of organometallic chemistry.
Materials chemistry is the preparation, characterization, and understanding of substances with a useful function.
The field is a new breadth of study in graduate programs, and it integrates elements from all classical areas of
chemistry with a focus on fundamental issues that are unique to materials. Primary systems of study include the
chemistry of condensed phases (solids, liquids, polymers) and interfaces between different phases.
Neurochemistry is the study of neurochemicals; including transmitters, peptides, proteins, lipids, sugars, and
nucleic acids; their interactions, and the roles they play in forming, maintaining, and modifying the nervous
system.
Nuclear chemistry is the study of how subatomic particles come together and make nuclei. Modern Transmutation
is a large component of nuclear chemistry, and the table of nuclides is an important result and tool for this field.
Organic chemistry is the study of the structure, properties, composition, mechanisms, and reactions of organic
compounds. An organic compound is defined as any compound based on a carbon skeleton.
Physical chemistry is the study of the physical and fundamental basis of chemical systems and processes. In
particular, the energetics and dynamics of such systems and processes are of interest to physical chemists.
Important areas of study include chemical thermodynamics, chemical kinetics, electrochemistry, statistical
mechanics, spectroscopy, and more recently, astrochemistry.[49] Physical chemistry has large overlap with
molecular physics. Physical chemistry involves the use of infinitesimal calculus in deriving equations. It is
usually associated with quantum chemistry and theoretical chemistry. Physical chemistry is a distinct discipline
from chemical physics, but again, there is very strong overlap.
Theoretical chemistry is the study of chemistry via fundamental theoretical reasoning (usually within mathematics
or physics). In particular the application of quantum mechanics to chemistry is called quantum chemistry. Since
the end of the Second World War, the development of computers has allowed a systematic development of
computational chemistry, which is the art of developing and applying computer programs for solving chemical
problems. Theoretical chemistry has large overlap with (theoretical and experimental) condensed matter physics
and molecular physics.
Other disciplines within chemistry are traditionally grouped by the type of matter being studied or the kind of study.
These include inorganic chemistry, the study of inorganic matter; organic chemistry, the study of organic (carbon
based) matter; biochemistry, the study of substances found in biological organisms; physical chemistry, the study of
chemical processes using physical concepts such as thermodynamics and quantum mechanics; and analytical
chemistry, the analysis of material samples to gain an understanding of their chemical composition and structure.
Many more specialized disciplines have emerged in recent years, e.g. neurochemistry the chemical study of the
nervous system (see subdisciplines).
Other fields include agrochemistry, astrochemistry (and cosmochemistry), atmospheric chemistry, chemical
engineering, chemical biology, chemo-informatics, electrochemistry, environmental chemistry, femtochemistry,
29
Chemistry
flavor chemistry, flow chemistry, geochemistry, green chemistry, histochemistry, history of chemistry,
hydrogenation chemistry, immunochemistry, marine chemistry, materials science, mathematical chemistry,
mechanochemistry, medicinal chemistry, molecular biology, molecular mechanics, nanotechnology, natural product
chemistry, oenology, organometallic chemistry, petrochemistry, pharmacology, photochemistry, physical organic
chemistry, phytochemistry, polymer chemistry, radiochemistry, solid-state chemistry, sonochemistry,
supramolecular chemistry, surface chemistry, synthetic chemistry, thermochemistry, and many others.
Chemical industry
The chemical industry represents an important economic activity. The global top 50 chemical producers in 2004 had
sales of 587 billion US dollars with a profit margin of 8.1% and research and development spending of 2.1% of total
chemical sales.[50]
Professional societies
American Chemical Society
American Society for Neurochemistry
Chemical Institute of Canada
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Further reading
Popular reading
Atkins, P.W. Galileo's Finger (Oxford University Press) ISBN 0-19-860941-8
Atkins, P.W. Atkins' Molecules (Cambridge University Press) ISBN 0-521-82397-8
Kean, Sam. The Disappearing Spoon - and other true tales from the Periodic Table (Black Swan) London, 2010
ISBN 978-0-552-77750-6
Levi, Primo The Periodic Table (Penguin Books) [1975] translated from the Italian by Raymond Rosenthal
(1984) ISBN 978-0-141-39944-7
Stwertka, A. A Guide to the Elements (Oxford University Press) ISBN 0-19-515027-9
Introductory undergraduate text books
Atkins, P.W., Overton, T., Rourke, J., Weller, M. and Armstrong, F. Shriver and Atkins inorganic chemistry (4th
edition) 2006 (Oxford University Press) ISBN 0-19-926463-5
Chang, Raymond. Chemistry 6th ed. Boston: James M. Smith, 1998. ISBN 0-07-115221-0.
Clayden, Jonathan; Greeves, Nick; Warren, Stuart; Wothers, Peter (2001). Organic Chemistry (1st ed.). Oxford
University Press. ISBN978-0-19-850346-0.
Voet and Voet Biochemistry (Wiley) ISBN 0-471-58651-X
Advanced undergraduate-level or graduate text books
32
History of chemistry
History of chemistry
By 1000 BC, ancient 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,
making pigments for cosmetics and painting, extracting chemicals from plants for medicine and perfume, making
cheese, dying cloth, tanning leather, rendering fat into soap, making glass, and making alloys like bronze.
Early attempts to explain the nature of matter and its transformations failed. The protoscience of chemistry,
Alchemy, was also unsuccessful in explaining the nature of matter. However, by performing experiments and
recording the results the alchemist set the stage for modern chemistry. This distinction begins to emerge when a clear
differentiation was made between chemistry and alchemy by Robert Boyle in his work The Sceptical Chymist
(1661). Chemistry then becomes a full-fledged science when Antoine Lavoisier develops his law of conservation of
mass, which demands careful measurements and quantitative observations of chemical phenomena. So, while both
alchemy and chemistry are concerned with the nature of matter and its transformations, it is only the chemists who
apply the scientific method. The history of chemistry is intertwined with the history of thermodynamics, especially
through the work of Willard Gibbs.[1]
33
History of chemistry
34
Alchemy not only sought to turn base metals into gold, but especially
in a Europe rocked by bubonic plague, there was hope that alchemy
would lead to the development of medicines to improve people's
health. The holy grail of this strain of alchemy was in the attempts
made at finding the elixir of life, which promised eternal youth.
Neither the elixir nor the philosopher's stone were ever found. Also,
characteristic of alchemists was the belief that there was in the air an
"ether" which breathed life into living things. Practitioners of alchemy
included Isaac Newton, who remained one throughout his life.
History of chemistry
35
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. 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.
Early chemists
In the Arab World, the Muslims were translating the works of the
ancient Greeks and Egyptians into Arabic and were experimenting with
scientific ideas.[8] 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 Jbir ibn Hayyn (known as "Geber" in Europe), who
is "considered as the father of chemistry".[9] [10] [11] [12] 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.[13] 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.[14] He
also refined the theory of five classical elements into the theory of
seven alchemical elements after identifying mercury and sulfur as
chemical elements.[15]
History of chemistry
36
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, decensory, 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.
For the more honest practitioners in Europe, alchemy became an intellectual
pursuit after early Arabic alchemy became available through Latin translation,
and over time, they got better at it. Paracelsus (14931541), 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.
Practical attempts to improve the refining of ores and their extraction to smelt
metals was an important source of information for early chemists, among
them Georg Agricola (14941555), who published his great work De re
Agricola, author of De re metallica
metallica in 1556. 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.
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.[21] In 1615 Jean Beguin publishes the Tyrocinium Chymicum, an
early chemistry textbook, and in it draws the first-ever chemical equation.[22]
Robert Boyle (16271691) is considered to have refined the modern
scientific method for alchemy and to have separated chemistry further
from alchemy.[23] Robert Boyle was an atomist, but favoured the word
corpuscle over atoms. He comments that the finest division of matter
where the properties are retained is at the level of corpuscles. Boyle
was credited with the discovery of Boyle's Law. He is also credited for
his landmark publication The Sceptical Chymist, where he attempts to
develop an atomic theory of matter, with no small degree of success.
He laid the foundations for the Chemical Revolution with his
mechanical corpuscular philosophy, which in turn relied heavily on the
alchemical corpuscular theory and experimental method dating back to
the alchemist Jbir ibn Hayyn.[24]
Despite all these advances, the person celebrated as the "father of
modern chemistry" is Antoine Lavoisier who developed his law of
conservation of mass in 1789, also called Lavoisier's Law.[25] With
this, chemistry acquired a strict quantitative nature, allowing reliable
predictions to be made.
History of chemistry
37
Joseph Proust proposed the law of definite proportions, which states that elements always combine in small, whole
number ratios to form compounds.[29] In 1800, Alessandro Volta devised the first chemical battery, thereby founding
the discipline of electrochemistry.[30] In 1803, John Dalton proposed Dalton's Law, which describes relationship
between the components in a mixture of gases and the relative pressure each contributes to that of the overall
mixture.[31]
Antoine Lavoisier
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
Lavoisier, who is regarded as the "father of modern chemistry",
particularly for his discovery of the law of conservation of mass, and
his refutation of the phlogiston theory of combustion in 1783.
(Phlogiston was supposed to be an imponderable substance liberated
by flammable materials in burning.) 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. He regarded heat as a form of
motion, and stated the idea of conservation of matter.
History of chemistry
38
For many decades, the list of known chemical elements had been
steadily increasing. A great breakthrough in making sense of this
long list (as well as in understanding the internal structure of
atoms as discussed below) was Dmitri Mendeleev and Lothar
Meyer's development of the periodic table, and particularly
Mendeleev's use of it to predict the existence and the properties of
germanium, gallium, and scandium, which Mendeleev called
ekasilicon, ekaaluminium, and ekaboron respectively. Mendeleev
made his prediction in 1870; gallium was discovered in 1875, and
was found to have roughly the same properties that Mendeleev
predicted for it.
History of chemistry
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.
After the discovery by Ernest Rutherford and Niels Bohr of the atomic structure in 1912, and by Marie and Pierre
Curie of radioactivity, scientists had to change their viewpoint on the nature of matter. The experience acquired by
chemists was no longer pertinent to the study of the whole nature of matter but only to aspects related to the electron
cloud surrounding the atomic nuclei and the movement of the latter in the electric field induced by the former (see
Born-Oppenheimer approximation). The range of chemistry was thus restricted to the nature of matter around us in
conditions which are not too far (or exceptionally far) from standard conditions for temperature and pressure and in
cases where the exposure to radiation is not too different from the natural microwave, visible or UV radiations on
Earth. Chemistry was therefore re-defined as the science of matter that deals with the composition, structure, and
properties of substances and with the transformations that they undergo. However the meaning of matter used here
relates explicitly to substances made of atoms and molecules, disregarding the matter within the atomic nuclei and its
nuclear reaction or matter within highly ionized plasmas. This does not mean that chemistry is never involved with
plasma or nuclear sciences or even bosonic fields nowadays, since areas such as Quantum Chemistry and Nuclear
Chemistry are currently well developed and formally recognized sub-fields of study under the Chemical sciences
(Chemistry), but what is now formally recognized as subject of study under the Chemistry category as a science is
always based on the use of concepts that describe or explain phenomena either from matter or to matter in the atomic
or molecular scale, including the study of the behavior of many molecules as an aggregate or the study of the effects
of a single proton on a single atom, but excluding phenomena that deal with different (more "exotic") types of matter
(e.g. Bose-Einstein condensate, Higgs Boson, dark matter, naked singularity, etc.) and excluding principles that refer
to intrinsic abstract laws of nature in which their concepts can be formulated completely without a precise formal
molecular or atomic paradigmatic view (e.g. Quantum Chromodynamics, Quantum Electrodynamics, String Theory,
parts of Cosmology (see Cosmochemistry), certain areas of Nuclear Physics (see Nuclear Chemistry),etc.).
Nevertheless the field of chemistry is still, on our human scale, very broad and the claim that chemistry is
everywhere is accurate.
Quantum chemistry
Some view the birth of quantum chemistry in the discovery of the Schrdinger equation and its application to the
hydrogen atom in 1926. However, the 1927 article of Walter Heitler and Fritz London[33] is often recognised as the
first milestone in the history of quantum chemistry.[34] 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 Hckel, Douglas Hartree, Vladimir Aleksandrovich Fock, to cite a few.
Still, skepticism remained as to the general power of quantum mechanics applied to complex chemical systems. The
situation around 1930 is described by Paul Dirac:[35]
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 the 1940s many physicists turned from molecular or atomic physics to nuclear physics (like J. Robert
Oppenheimer or Edward Teller). In 1951, a milestone article in quantum chemistry is the seminal paper of Clemens
C. J. Roothaan on Roothaan equations.[36] It opened the avenue to the solution of the self-consistent field equations
39
History of chemistry
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.
An important piece in the double helix puzzle was solved by one of Pauling's student 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.
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
40
History of chemistry
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.
Notes
[1] Selected Classic Papers from the History of Chemistry (http:/ / web. lemoyne. edu/ ~giunta/ papers. html)
[2] 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."
[3] Lucretius (50 BCE). "de Rerum Natura (On the Nature of Things)" (http:/ / classics. mit. edu/ Carus/ nature_things. html). The Internet
Classics Archive. Massachusetts Institute of Technology. . Retrieved 2007-01-09.
[4] Simpson, David (29 June 2005). "Lucretius (c. 99 - c. 55 BCE)" (http:/ / www. iep. utm. edu/ l/ lucretiu. htm). The Internet History of
Philosophy. . Retrieved 2007-01-09.
[5] 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."
[6]
[7]
[8]
[9]
Brock, William H. (1992). The Fontana History of Chemistry. London, England: Fontana Press. pp.3233. ISBN0006861733.
Brock, William H. (1992). The Fontana History of Chemistry. London, England: Fontana Press. ISBN0006861733.
The History of Ancient Chemistry (http:/ / realscience. breckschool. org/ upper/ fruen/ files/ Enrichmentarticles/ files/ History. html)
Derewenda, ZS (2007). "On wine, chirality and crystallography". Acta Crystallographica Section A: Foundations of Crystallography 64 (Pt
1): 246258 [247]. doi:10.1107/S0108767307054293. PMID18156689.
[10] John Warren (2005). "War and the Cultural Heritage of Iraq: a sadly mismanaged affair", Third World Quarterly, Volume 26, Issue 4 & 5, p.
815-830.
[11] Dr. A. Zahoor (1997), JABIR IBN HAIYAN (Jabir) (http:/ / www. unhas. ac. id/ ~rhiza/ saintis/ haiyan. html), University of Indonesia
[12] Paul Vallely, How Islamic inventors changed the world (http:/ / news. independent. co. uk/ world/ science_technology/ article350594. ece),
The Independent
[13] Kraus, Paul, Jbir ibn Hayyn, Contribution l'histoire des ides scientifiques dans l'Islam. I. Le corpus des crits jbiriens. II. Jbir et la
science grecque,. Cairo (1942-1943). Repr. By Fuat Sezgin, (Natural Sciences in Islam. 67-68), Frankfurt. 2002:
To form an idea of the historical place of Jabirs 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
41
History of chemistry
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 Jabirs 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, one notes with him a balance between theoretical teaching and practical teaching, between the
`ilm and the `amal. In vain one would seek in the Greek texts a work as systematic as that which is
presented for example in the Book of Seventy.
(cf. Ahmad Y Hassan. "A Critical Reassessment of the Geber Problem: Part Three" (http:/ / www. history-science-technology. com/ Geber/
Geber 3. htm). . Retrieved 2008-08-09.)
[14] Will Durant (1980). The Age of Faith (The Story of Civilization, Volume 4), p. 162-186. Simon & Schuster. ISBN 0671012002.
[15] Strathern, Paul. (2000), Mendeleyevs Dream the Quest for the Elements, New York: Berkley Books
[16] Research Committee of Strasburg University, Imam Jafar Ibn Muhammad As-Sadiq A.S. The Great Muslim Scientist and Philosopher,
translated by Kaukab Ali Mirza, 2000. Willowdale Ont. ISBN 0969949014.
[17] Felix Klein-Frank (2001), "Al-Kindi", in Oliver Leaman & Hossein Nasr, History of Islamic Philosophy, p. 174. London: Routledge.
[18] Marmura Michael E., Nasr Seyyed Hossein (1965). "An Introduction to Islamic Cosmological Doctrines. Conceptions of Nature and
Methods Used for Its Study by the Ikhwan Al-Safa'an, Al-Biruni, and Ibn Sina by Seyyed Hossein Nasr". Speculum 40 (4): 744746.
doi:10.2307/2851429. JSTOR2851429.
[19] Robert Briffault (1938). The Making of Humanity, p. 196-197.
[20] Alakbarov Farid (2001). "A 13th-Century Darwin? Tusi's Views on Evolution" (http:/ / azer. com/ aiweb/ categories/ magazine/ 92_folder/
92_articles/ 92_tusi. html). Azerbaijan International 9: 2. .
[21] Asarnow, Herman (2005-08-08). "Sir Francis Bacon: Empiricism" (http:/ / faculty. up. edu/ asarnow/ eliz4. htm). An Image-Oriented
Introduction to Backgrounds for English Renaissance Literature. University of Portland. . Retrieved 2007-02-22.
[22] Crosland, M.P. (1959). "The use of diagrams as chemical 'equations' in the lectures of William Cullen and Joseph Black." Annals of Science,
Vol 15, No. 2, Jun.
[23] Robert Boyle (http:/ / understandingscience. ucc. ie/ pages/ sci_robertboyle. htm)
[24] Ursula Klein (July 2007). "Styles of Experimentation and Alchemical Matter Theory in the Scientific Revolution". Metascience (Springer)
16 (2): 247256 [247]. doi:10.1007/s11016-007-9095-8. ISSN1467-9981
[25] Lavoisier, Antoine (1743-1794) -- from Eric Weisstein's World of Scientific Biography (http:/ / scienceworld. wolfram. com/ biography/
Lavoisier. html), ScienceWorld
[26] Cooper, Alan (1999). "Joseph Black" (http:/ / web. archive. org/ web/ 20060410074412/ http:/ / www. chem. gla. ac. uk/ dept/ black. htm).
History of Glasgow University Chemistry Department. University of Glasgow Department of Chemistry. Archived from the original (http:/ /
www. chem. gla. ac. uk/ dept/ black. htm) on 2006-04-10. . Retrieved 2006-02-23.
[27] "Joseph Priestley" (http:/ / www. chemheritage. org/ classroom/ chemach/ forerunners/ priestley. html). Chemical Achievers: The Human
Face of Chemical Sciences. Chemical Heritage Foundation. 2005. . Retrieved 2007-02-22.
[28] "Carl Wilhelm Scheele" (http:/ / mattson. creighton. edu/ History_Gas_Chemistry/ Scheele. html). History of Gas Chemistry. Center for
Microscale Gas Chemistry, Creighton University. 2005-09-11. . Retrieved 2007-02-23.
[29] "Proust, Joseph Louis (1754-1826)" (http:/ / www. euchems. org/ Distinguished/ 19thCentury/ proustlouis. asp). 100 Distinguished
Chemists. European Association for Chemical and Molecular Science. 2005. . Retrieved 2007-02-23.
[30] "Inventor Alessandro Volta Biography" (http:/ / www. ideafinder. com/ history/ inventors/ volta. htm). The Great Idea Finder. The Great
Idea Finder. 2005. . Retrieved 2007-02-23.
[31] "John Dalton" (http:/ / www. chemheritage. org/ classroom/ chemach/ periodic/ dalton. html). Chemical Achievers: The Human Face of
Chemical Sciences. Chemical Heritage Foundation. 2005. . Retrieved 2007-02-22.
[32] Pullman, Bernard (2004). The Atom in the History of Human Thought. Reisinger, Axel. USA: Oxford University Press Inc.
ISBN0195114477.
[33] W. Heitler and F. London, Wechselwirkung neutraler Atome und Homopolare Bindung nach der Quantenmechanik, Z. Physik, 44, 455
(1927).
[34] Quantum chemistry (http:/ / www. fact-archive. com/ encyclopedia/ Quantum_chemistry)
[35] P.A.M. Dirac, Quantum Mechanics of Many-Electron Systems, Proc. R. Soc. London, A 123, 714 (1929).
[36] C.C.J. Roothaan, A Study of Two-Center Integrals Useful in Calculations on Molecular Structure, J. Chem. Phys., 19, 1445 (1951).
[37] Watson, J. and Crick, F., "Molecular Structure of Nucleic Acids" (http:/ / www. nature. com/ nature/ dna50/ watsoncrick. pdf) Nature, April
25, 1953, p 7378
42
History of chemistry
References
Selected classic papers from the history of chemistry (http://web.lemoyne.edu/~giunta/papers.html)
Biographies of chemists (http://www.liv.ac.uk/Chemistry/Links/refbiog.html)
Eric R. Scerri, The Periodic Table: Its Story and Its Significance, Oxford University Press, 2006.
Further reading
Servos, John W., Physical chemistry from Ostwald to Pauling : the making of a science in America (http://books.
google.com/books?id=1UZjU2WfLAoC&printsec=frontcover), Princeton, N.J. : Princeton University Press,
1990. ISBN 0691085668
Documentaries
BBC (2010). Chemistry: A Volatile History.
External links
ChemisLab (http://www.chemislab.com/chemists-of-the-past/) - Chemists of the Past
SHAC: Society for the History of Alchemy and Chemistry (http://www.ambix.org/)
Origins
Medieval Islamic alchemy was based on previous alchemical writers, firstly those writing in Greek, but also using
Indian, Jewish, and Christian sources. According to Anawati, the alchemy practiced in Egypt around the second
century BCE was a mixture of Hermetic or gnostic elements and Greek philosophy. Later, with Zosimos of
Panopolis, alchemy acquired mystical and religious elements.[4]
The sources of Islamic alchemy were transmitted to the Muslim world mainly in Egypt, especially in Alexandria, but
also in the cities of Harran, Nisibin, and Edessa in western Mesopotamia.[5]
43
44
Jafar al-diq
Jafar al-diq, the son of Muammad al-Bqir, lived in Medina. He is said to have been the teacher of Jbir ibn
ayyn. A number of pseudepigraphical works have been attributed to him.[8]
Ab Bakr al-Rz
Ab Bakr al-Rz (Latin: Rhazes), born around 864 in Rey, was mainly known as a doctor. He wrote a number of
alchemical works, including Sirr al-asrr (Latin: Secretum secretorum.)[10] [11]
45
Ibn Umayl
Muammad ibn Umayl al-Tamm was an 11th-century alchemist. One of his surviving works is Kitb al-m
al-waraq wa-l-ar al-najmiyya (The Book on Silvered Water and Starry Earth.) This work is a commentary on his
poem Rislat al-shams wa-t-hill (The Epistle on the Sun and the Crescent) and contains numerous quotations from
ancient authors.[12]
Fire Earth
Moist Air
Water
Jbir analyzed each Aristotelian element in terms of four basic qualities of hotness, coldness, dryness, and moistness.
For example, fire is a substance that is hot and dry, as shown in the table.[13] (This scheme was also used by
Aristotle.)[14] [15] According to Jbir, in each metal two of these qualities were interior and two were exterior. For
example, lead was externally cold and dry but internally hot and moist; gold, on the other hand, was externally hot
and moist but internally cold and dry. He believed that metals were formed in the Earth by fusion of sulfur (giving
the hot and dry qualities) with mercury (giving the cold and moist.) These elements, mercury and sulfur, should be
thought of as not the ordinary elements but ideal, hypothetical substances. Which metal is formed depends on the
purity of the mercury and sulfur and the proportion in which they come together.[13] The later alchemist al-Rz
followed Jbir's mercury-sulfur theory, but added a third, salty, component.[16]
Thus, Jbir theorized, by rearranging the qualities of one metal, a different metal would result.[17] By this reasoning,
the search for the philosopher's stone was introduced to Western alchemy.[18] [19] Jbir developed an elaborate
numerology whereby the root letters of a substance's name in Arabic, when treated with various transformations,
held correspondences to the element's physical properties.[13]
distillation,
calcination,
solution,
evaporation,
crystallization,
sublimation,
filtration,
amalgamation,
and ceration (a process for making solids pasty or fusible.)[20]
Some of these operations (calcination, solution, filtration, crystallization, sublimation and distillation) are also
known to have been practiced by pre-Islamic Alexandrian alchemists.[21]
In his Secretum secretorum, Al-Rz mentions the following equipment:[22]
Tools for melting substances (li-tadhwb): hearth (kr), bellows (minfkh aw ziqq), crucible (bawtaqa), the bt
bar bt (in Arabic) or botus barbatus (in Latin), ladle (mighrafa aw milaqa), tongs (msik aw kalbatn), scissors
(miqa), hammer (mukassir), file (mibrad).
References
[1] "alchemy", entry in The Oxford English Dictionary, J. A. Simpson and E. S. C. Weiner, vol. 1, 2nd ed., 1989, ISBN 0-19-861213-3.
[2] p. 854, "Arabic alchemy", Georges C. Anawati, pp. 853-885 in Encyclopedia of the history of Arabic science, eds. Roshdi Rashed and Rgis
Morelon, London: Routledge, 1996, vol. 3, ISBN 0415124123.
[3] Burckhardt, Titus (1967). Alchemy: science of the cosmos, science of the soul. Stuart & Watkins. p. 46
[4] Anawati 1996, pp. 854-863.
[5] pp. 67-68, Holmyard 1990.
[6] pp. 63-66, Alchemy, E. J. Holmyard, New York: Dover Publications, Inc., 1990 (reprint of 1957 Penguin Books edition), ISBN
0-486-26298-7.
[7] M. Ullmann, "hlid b. Yazd b. Muwiya, ab hshim.", in Encyclopaedia of Islam, second edition, edited by P. Bearman, Th. Bianquis, C.
E. Bosworth, E. van Donzel, and W.P. Heinrichs, Brill, 2011. Brill Online. Accessed 20 January 2011.
<http://www.brillonline.nl/subscriber/entry?entry=islam_SIM-4151>
[8] Anawati 1996, p. 864.
[9] pp. 68-82, Holmyard 1990.
[10] pp. 867-879, Anawati 1996.
[11] pp. 86-92, Holmyard 1990.
[12] pp. 870-872, Anawati 1996.
[13] pp. 74-82, Holmyard 1990.
[14] Holmyard 1990, pp. 21-22.
[15] Aristotle, On Generation and Corruption, II.3, 330a-330b.
[16] Holmyard 1990, p. 88.
[17] Burckhardt, Titus (1967). Alchemy: science of the cosmos, science of the soul. Stuart & Watkins. p. 29
[18] Ragai, Jehane (1992). "The Philosopher's Stone: Alchemy and Chemistry". Journal of Comparative Poetics 12 (Metaphor and Allegory in
the Middle Ages): 5877
[19] Holmyard, E. J. (1924). "Maslama al-Majriti and the Rutbatu'l-Hakim". Isis 6 (3): 293305
[20] p. 89, Holmyard 1990.
[21] p. 23, A short history of chemistry, James Riddick Partington, 3rd ed., Courier Dover Publications, 1989, ISBN 0486659771.
[22] Anawati 1996, p. 868
External links
"How Greek Science Passed to the Arabs" (http://www.aina.org/books/hgsptta.htm) by De Lacy O'Leary
46
Timeline of chemistry
47
Timeline of chemistry
The timeline of chemistry lists important works, discoveries, ideas,
inventions, and experiments that significantly changed humanity's
understanding of the modern science known as chemistry, defined as
the scientific study of the composition of matter and of its interactions.
The history of chemistry in its modern form arguably began with the
English scientist Robert Boyle, though its roots can be traced back to
the earliest recorded history.
Early ideas that later became incorporated into the modern science of
chemistry come from two main sources. Natural philosophers (such as
Aristotle and Democritus) used deductive reasoning in an attempt to
explain the behavior of the world around them. Alchemists (such as
Geber and Rhazes) were people who used experimental techniques in
an attempt to extend the life or perform material conversions, such as
turning base metals into gold.
In the 17th century, a synthesis of the ideas of these two disciplines,
that is the deductive and the experimental, leads to the development of
a process of thinking known as the scientific method. With the
introduction of the scientific method, the modern science of chemistry
was born.
An image from John Dalton's A New System of
Pre-17th century
Prior to the acceptance of the scientific method and its application to the field of
chemistry, it is somewhat controversial to consider many of the people listed
below as "chemists" in the modern sense of the word. However, the ideas of
certain great thinkers, either for their prescience, or for their wide and long-term
acceptance, bear listing here.
c. 3000 BCE
Egyptians formulate the theory of the Ogdoad, or the primordial forces,
from which all was formed. These were the elements of chaos, numbered
in eight, that existed before the creation of the sun.[2]
c. 1900 BCE
Hermes Trismegistus, semi-mythical ancient Egyptian adept king, is
thought to have founded the art of alchemy.[3]
c. 1200 BCE
Timeline of chemistry
48
c. 360 BCE
Plato coins term elements (stoicheia) and in his dialogue
Timaeus, which includes a discussion of the composition of
inorganic and organic bodies and is a rudimentary treatise on
chemistry, assumes that the minute particle of each element had
a special geometric shape: tetrahedron (fire), octahedron (air),
icosahedron (water), and cube (earth).[8]
c. 350 BCE
Aristotle, expanding on Empedocles, proposes idea of a
substance as a combination of matter and form. Describes theory
of the Five Elements, fire, water, earth, air, and aether. This
theory is largely accepted throughout the western world for over
1000 years.[9]
c. 50 BCE
Lucretius publishes De Rerum Natura, a poetic description of the ideas of Atomism.[10]
c. 300
Zosimos of Panopolis writes some of the oldest known books on alchemy, which he defines as the study of the
composition of waters, movement, growth, embodying and disembodying, drawing the spirits from bodies and
bonding the spirits within bodies.[11]
c. 770
Abu Musa Jabir ibn Hayyan (aka Geber), an Arab/Persian alchemist who is "considered by many to be the
father of chemistry",[12] [13] [14] develops an early experimental method for chemistry, and isolates numerous
acids, including hydrochloric acid, nitric acid, citric acid, acetic acid, tartaric acid, and aqua regia.[15]
c. 1000
Ab al-Rayhn al-Brn[16] and Avicenna,[17] both Persian chemists, refute the practice of alchemy and the
theory of the transmutation of metals.
c. 1167
Alchemists in the School of Salerno make the first references to the distillation of wine.[18]
c. 1220
Timeline of chemistry
Robert Grosseteste publishes several Aristotelian commentaries where he lays out an early framework for the
scientific method.[19]
c 1250
Tadeo Alderotti develops Fractional distillation, which is much more effective than its predecessors.[20]
c 1260
St Albertus Magnus discovers Arsenic[21] and Silver nitrate.[22] He also made one of the first references to
sulfuric acid.[23]
c. 1267
Roger Bacon publishes Opus Maius, which among other things, proposes an early form of the scientific
method, and contains results of his experiments with gunpowder.[24]
c. 1310
Pseudo-Geber, an anonymous Spanish alchemist who wrote under the name of Geber, publishes several books
that establish the long-held theory that all metals were composed of various proportions of sulfur and
mercury.[25] He is one of the first to describe nitric acid, aqua regia, and aqua fortis.[26]
c. 1530
Paracelsus develops the study of iatrochemistry, a subdiscipline of alchemy dedicated to extending the life,
thus being the roots of the modern pharmaceutical industry. It is also claimed that he is the first to use the
word "chemistry".[11]
1597
Andreas Libavius publishes Alchemia, a prototype chemistry textbook.[27]
49
Timeline of chemistry
50
1661
Robert Boyle publishes The Sceptical Chymist, a treatise on the distinction
between chemistry and alchemy. It contains some of the earliest modern
ideas of atoms, molecules, and chemical reaction, and marks the beginning
of the history of modern chemistry.[33]
1662
Robert Boyle proposes Boyle's Law, an experimentally based description
of the behavior of gases, specifically the relationship between pressure and
volume.[33]
1735
Swedish chemist Georg Brandt analyzes a dark blue pigment found in
copper ore. Brandt demonstrated that the pigment contained a new
element, later named cobalt.
Title page of The Sceptical Chymist
by Robert Boyle (162791)
1754
Joseph Black isolates carbon dioxide, which he called "fixed air".[34]
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.[35]
1758
Joseph Black formulates the concept of latent heat to explain the
thermochemistry of phase changes.[36]
1766
Henry Cavendish discovers hydrogen as a colorless, odourless gas that burns and can form an explosive
mixture with air.
17731774
Carl Wilhelm Scheele and Joseph Priestly independently isolate oxygen, called by Priestly "dephlogisticated
air" and Scheele "fire air".[37] [38]
Timeline of chemistry
51
1778
Antoine Lavoisier, considered "The father of modern chemistry",[39]
recognizes and names oxygen, and recognizes its importance and role in
combustion.[40]
1787
Antoine Lavoisier publishes Mthode de nomenclature chimique, the first
modern system of chemical nomenclature.[40]
1787
Jacques Charles proposes Charles's Law, a corollary of Boyle's Law,
describes relationship between temperature and volume of a gas.[41]
1789
Antoine Lavoisier publishes Trait lmentaire de Chimie, the first
modern chemistry textbook. It is a complete survey of (at that time)
modern chemistry, including the first concise definition of the law of
conservation of mass, and thus also represents the founding of the
discipline of stoichiometry or quantitative chemical analysis.[40] [42]
Antoine-Laurent de Lavoisier
(174394) is considered the "Father
of Modern Chemistry".
1797
Joseph Proust proposes the law of definite proportions, which states that elements always combine in small,
whole number ratios to form compounds.[43]
1800
Alessandro Volta devises the first chemical battery, thereby founding the discipline of electrochemistry.[44]
19th century
1803
John Dalton proposes Dalton's Law, which describes relationship
between the components in a mixture of gases and the relative
pressure each contributes to that of the overall mixture.[45]
1805
Joseph Louis Gay-Lussac discovers that water is composed of
two parts hydrogen and one part oxygen by volume.[46]
1808
Joseph Louis Gay-Lussac collects and discovers several
chemical and physical properties of air and of other gases,
including experimental proofs of Boyle's and Charles's laws, and
of relationships between density and composition of gases.[47]
1808
John Dalton publishes New System of Chemical Philosophy,
which contains first modern scientific description of the atomic
theory, and clear description of the law of multiple proportions.[45]
1808
Jns Jakob Berzelius publishes Lrbok i Kemien in which he proposes modern chemical symbols and notation,
and of the concept of relative atomic weight.[48]
Timeline of chemistry
52
1811
Amedeo Avogadro proposes Avogadro's law, that equal volumes of gases under constant temperature and
pressure contain equal number of molecules.[49]
1825
Friedrich Whler and Justus von Liebig perform the first confirmed
discovery and explanation of isomers, earlier named by Berzelius.
Working with cyanic acid and fulminic acid, they correctly deduce
that isomerism was caused by differing arrangements of atoms within
a molecular structure.[50]
1827
Timeline of chemistry
Friedrich August Kekul von Stradonitz proposes that carbon is tetravalent, or forms exactly four chemical
bonds.[59]
18591860
Gustav Kirchhoff and Robert Bunsen lay the foundations of spectroscopy as a means of chemical analysis,
which lead them to the discovery of caesium and rubidium. Other workers soon used the same technique to
discover indium, thalium, and helium.[60]
1860
Stanislao Cannizzaro, resurrecting Avogadro's ideas regarding diatomic molecules, compiles a table of atomic
weights and presents it at the 1860 Karlsruhe Congress, ending decades of conflicting atomic weights and
molecular formulas, and leading to Mendeleev's discovery of the periodic law.[61]
1862
Alexander Parkes exhibits Parkesine, one of the earliest synthetic polymers, at the International Exhibition in
London. This discovery formed the foundation of the modern plastics industry.[62]
1862
Alexandre-Emile Bguyer de Chancourtois publishes the telluric helix, an early, three-dimensional version of
the Periodic Table of the Elements.[63]
1864
John Newlands proposes the law of octaves, a precursor to the Periodic Law.[63]
1864
Lothar Meyer develops an early version of the periodic table, with 28 elements organized by valence.[64]
1864
Cato Maximilian Guldberg and Peter Waage, building on Claude Louis Berthollets ideas, proposed the Law of
Mass Action.[65] [66] [67]
1865
Johann Josef Loschmidt determines exact number of molecules in a mole, later named Avogadro's Number.[68]
1865
Friedrich August Kekul von Stradonitz, based partially on the work of Loschmidt and others, establishes
structure of benzene as a six carbon ring with alternating single and double bonds.[59]
1865
Adolf von Baeyer begins work on indigo dye, a milestone in modern industrial organic chemistry which
revolutionizes the dye industry.[69]
53
Timeline of chemistry
54
1869
Dmitri Mendeleev publishes the first modern periodic table, with
the 66 known elements organized by atomic weights. The
strength of his table was its ability to accurately predict the
properties of as-yet unknown elements.[63] [64]
1873
Jacobus Henricus van 't Hoff and Joseph Achille Le Bel,
working independently, develop a model of chemical bonding
that explains the chirality experiments of Pasteur and provides a
physical cause for optical activity in chiral compounds.[70]
1876
Josiah Willard Gibbs publishes On the Equilibrium of
Heterogeneous Substances, a compilation of his work on
thermodynamics and physical chemistry which lays out the
concept of free energy to explain the physical basis of chemical
equilibria.[71]
1877
Ludwig Boltzmann establishes statistical derivations of many important physical and chemical concepts,
including entropy, and distributions of molecular velocities in the gas phase.[72]
1883
Svante Arrhenius develops ion theory to explain conductivity in electrolytes.[73]
1884
Jacobus Henricus van 't Hoff publishes tudes de Dynamique chimique, a seminal study on chemical
kinetics.[74]
1884
Hermann Emil Fischer proposes structure of purine, a key structure in many biomolecules, which he later
synthesized in 1898. Also begins work on the chemistry of glucose and related sugars.[75]
1884
Henry Louis Le Chatelier develops Le Chatelier's principle, which explains the response of dynamic chemical
equilibria to external stresses.[76]
1885
Eugene Goldstein names 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.[77]
1893
Alfred Werner discovers the octahedral structure of cobalt complexes, thus establishing the field of
coordination chemistry.[78]
18941898
William Ramsay discovers the noble gases, which fill a large and unexpected gap in the periodic table and led
to models of chemical bonding.[79]
1897
J. J. Thomson discovers the electron using the cathode ray tube.[80]
Timeline of chemistry
55
1898
Wilhelm Wien demonstrates 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.[81]
1898
Maria Sklodowska-Curie and Pierre Curie isolate radium and polonium from pitchblende.[82]
c. 1900
Ernest Rutherford discovers the source of radioactivity as decaying atoms; coins terms for various types of
radiation.[83]
20th century
1903
Mikhail Semyonovich Tsvet invents chromatography, an important analytic technique.[84]
1904
Hantaro Nagaoka proposes an early nuclear model of the atom, where electrons orbit a dense massive
nucleus.[85]
1905
Fritz Haber and Carl Bosch develop the Haber process for making ammonia from its elements, a milestone in
industrial chemistry with deep consequences in agriculture.[86]
1905
Albert Einstein explains Brownian motion in a way that definitively proves atomic theory.[87]
1907
Leo Hendrik Baekeland invents bakelite, one of the first commercially successful plastics.[88]
1909
Robert Millikan measures the charge of individual electrons with
unprecedented accuracy through the oil drop experiment, confirming that
all electrons have the same charge and mass.[89]
1909
S. P. L. Srensen invents the pH concept and develops methods for
measuring acidity.[90]
1911
Antonius Van den Broek proposes the idea that the elements on the
periodic table are more properly organized by positive nuclear charge
rather than atomic weight.[91]
1911
Timeline of chemistry
56
1912
William Henry Bragg and William Lawrence Bragg propose Bragg's law and establish the field of X-ray
crystallography, an important tool for elucidating the crystal structure of substances.[93]
1912
Peter Debye develops the concept of molecular dipole to describe asymmetric charge distribution in some
molecules.[94]
1913
Niels Bohr introduces 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
orbitals.[95]
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,[96]
1913
Frederick Soddy proposes the concept of isotopes, that elements with the same chemical properties may have
differing atomic weights.[97]
1913
J. J. Thomson expanding on the work of Wien, shows that charged subatomic particles can be separated by
their mass-to-charge ratio, a technique known as mass spectrometry.[98]
1916
Gilbert N. Lewis publishes "The Atom and the Molecule", the foundation of valence bond theory.[99]
1921
Otto Stern and Walther Gerlach establish concept of quantum mechanical spin in subatomic particles.[100]
1923
Gilbert N. Lewis and Merle Randall publish Thermodynamics and the Free Energy of Chemical Substances,
first modern treatise on chemical thermodynamics.[101]
1923
Gilbert N. Lewis develops the electron pair theory of acid/base reactions.[99]
1924
Louis de Broglie introduces the wave-model of atomic structure, based on the ideas of wave-particle
duality.[102]
1925
Wolfgang Pauli develops the exclusion principle, which states that no two electrons around a single nucleus
may have the same quantum state, as described by four quantum numbers.[103]
Timeline of chemistry
57
1926
Erwin Schrdinger proposes the Schrdinger equation, which provides a
mathematical basis for the wave model of atomic structure.[104]
1927
Werner Heisenberg develops the uncertainty principle which, among other things, explains the mechanics of
electron motion around the nucleus.[105]
1927
Fritz London and Walter Heitler apply quantum mechanics to explain covalent bonding in the hydrogen
molecule,[106] which marked the birth of quantum chemistry.[107]
c. 1930
Linus Pauling proposes Pauling's rules, which are key principles for the use of X-ray crystallography to deduce
molecular structure.[108]
1930
Wallace Carothers leads a team of chemists at DuPont who
invent nylon, one of the most commercially successful synthetic
polymers in history.[109]
1931
Erich Hckel proposes Hckel's rule, which explains when a
planar ring molecule will have aromatic properties.[110]
Model of two common forms of nylon
1931
Timeline of chemistry
Linus Pauling publishes The Nature of the Chemical Bond, a compilation of a decades worth of work on
chemical bonding. It is one of the most important modern chemical texts. It explains hybridization theory,
covalent bonding and ionic bonding as explained through electronegativity, and resonance as a means to
explain, among other things, the structure of benzene.[108]
1940
Edwin McMillan and Philip H. Abelson identify neptunium, the lightest and first synthesized transuranium
element, found in the products of uranium fission. McMillan would found a lab at Berkley that would be
involved in the discovery of many new elements and isotopes.[118]
1941
Glenn T. Seaborg takes over McMillan's work creating new atomic nuclei. Pioneers method of neutron capture
and later through other nuclear reactions. Would become the principal or co-discoverer of nine new chemical
elements, and dozens of new isotopes of existing elements.[118]
1945
Jacob A. Marinsky, Lawrence E. Glendenin, and Charles D. Coryell perform the first confirmed synthesis of
Promethium, filling in the last "gap" in the periodic table.[119]
19451946
Felix Bloch and Edward Mills Purcell develop the process of Nuclear Magnetic Resonance, an analytical
technique important in elucidating structures of molecules, especially in organic chemistry.[120]
1951
Linus Pauling uses X-ray crystallography to deduce the secondary structure of proteins.[108]
1952
Alan Walsh pioneers the field of atomic absorption spectroscopy, an important quantitative spectroscopy
method that allows one to measure specific concentrations of a material in a mixture.[121]
1952
Robert Burns Woodward, Geoffrey Wilkinson, and Ernst Otto Fischer discover the structure of ferrocene, one
of the founding discoveries of the field of organometallic chemistry.[122]
1953
James D. Watson and Francis Crick propose the structure of DNA, opening the door to the field of molecular
biology.[123]
1957
Jens Skou discovers Na/K-ATPase, the first ion-transporting enzyme.[124]
1958
Max Perutz and John Kendrew use X-ray crystallography to elucidate a protein structure, specifically Sperm
Whale myoglobin.[125]
1962
Neil Bartlett synthesizes xenon hexafluoroplatinate, showing for the first time that the noble gases can form
chemical compounds.[126]
1962
George Olah observes carbocations via superacid reactions.[127]
1964
Richard R. Ernst performs experiments that will lead to the development of the technique of Fourier
Transform NMR. This would greatly increase the sensitivity of the technique, and open the door for magnetic
58
Timeline of chemistry
59
1985
Harold Kroto, Robert Curl and Richard Smalley discover fullerenes, a
class of large carbon molecules superficially resembling the geodesic
dome designed by architect R. Buckminster Fuller.[141]
1991
Sumio Iijima uses 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.[142]
Buckminsterfullerene, C60
1994
First total synthesis of Taxol by Robert A. Holton and his group.[143] [144] [145]
1995
Eric Cornell and Carl Wieman produce the first BoseEinstein condensate, a substance that displays quantum
mechanical properties on the macroscopic scale.[146]
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Further reading
Servos, John W., Physical chemistry from Ostwald to Pauling : the making of a science in America (http://books.
google.com/books?id=1UZjU2WfLAoC&printsec=frontcover), Princeton, N.J. : Princeton University Press,
1990. ISBN 0691085668
External links
Chemical Achievers: The Human Face of the Chemical Sciences (http://www.chemheritage.org/classroom/
chemach/index.html)
Eric Weisstein's World of Scientific Biography (http://scienceworld.wolfram.com/biography/)
History of Gas Chemistry (http://mattson.creighton.edu/HistoryGasChemistry.html)
list of all Nobel Prize laureates (http://nobelprize.org/nobel_prizes/lists/all/)
History of Elements of the Periodic Table (http://www.ausetute.com.au/elemhist.html)
Chemsoc timeline (http://www.chemsoc.org/timeline/pages/timeline.html)
64
65
An illustration of the helium atom, depicting the nucleus (pink) and the electron cloud distribution (black). The nucleus (upper right) in helium-4 is
in reality spherically symmetric and closely resembles the electron cloud, although for more complicated nuclei this is not always the case. The
black bar is one angstrom (1010m or 100pm).
Classification
Properties
Mass range:
1.671027 to 4.521025kg
The atom is a basic unit of matter that consists of a dense central nucleus surrounded by a cloud of negatively
charged electrons. The atomic nucleus contains a mix of positively charged protons and electrically neutral neutrons
(except in the case of hydrogen-1, which is the only stable nuclide with no neutrons). The electrons of an atom are
bound to the nucleus by the electromagnetic force. Likewise, a group of atoms can remain bound to each other,
forming a molecule. An atom containing an equal number of protons and electrons is electrically neutral, otherwise it
has a positive charge if there are fewer electrons (electron deficiency) or negative charge if there are more electrons
(electron excess). A positively or negatively charged atom is known as an ion. An atom is classified according to the
number of protons and neutrons in its nucleus: the number of protons determines the chemical element, and the
number of neutrons determines the isotope of the element.[1]
Atom
The name atom comes from the Greek (atomos, indivisible) from - (a-, not) and (temn, I
cut)[2] , which means uncuttable, or indivisible, something that cannot be divided further.[3] The concept of an atom
as an indivisible component of matter was first proposed by early Indian and Greek philosophers. In the 17th and
18th centuries, chemists provided a physical basis for this idea by showing that certain substances could not be
further broken down by chemical methods. During the late 19th and early 20th centuries, physicists discovered
subatomic components and structure inside the atom, thereby demonstrating that the 'atom' was divisible. The
principles of quantum mechanics were used to successfully model the atom.[4] [5]
Atoms are minuscule objects with proportionately tiny masses. Atoms can only be observed individually using
special instruments such as the scanning tunneling microscope. Over 99.94% of an atom's mass is concentrated in the
nucleus,[6] with protons and neutrons having roughly equal mass. Each element has at least one isotope with unstable
nuclei that can undergo radioactive decay. This can result in a transmutation that changes the number of protons or
neutrons in a nucleus.[7] Electrons that are bound to atoms possess a set of stable energy levels, or orbitals, and can
undergo transitions between them by absorbing or emitting photons that match the energy differences between the
levels. The electrons determine the chemical properties of an element, and strongly influence an atom's magnetic
properties.
History
Atomism
The concept that matter is composed of discrete units and cannot be divided into arbitrarily tiny quantities has been
around for millennia, but these ideas were founded in abstract, philosophical reasoning rather than experimentation
and empirical observation. The nature of atoms in philosophy varied considerably over time and between cultures
and schools, and often had spiritual elements. Nevertheless, the basic idea of the atom was adopted by scientists
thousands of years later because it elegantly explained new discoveries in the field of chemistry.[8]
References to the concept of atoms date back to ancient Greece and India. In India, the jvika, Jain, and Crvka
schools of atomism may date back to the 6th century BCE.[9] The Nyaya and Vaisheshika schools later developed
theories on how atoms combined into more complex objects.[10] In the West, the references to atoms emerged in the
5th century BCE with Leucippus, whose student, Democritus, systematized his views. In approximately 450BCE,
Democritus coined the term tomos (Greek: ), which means "uncuttable" or "the smallest indivisible particle
of matter". Although the Indian and Greek concepts of the atom were based purely on philosophy, modern science
has retained the name coined by Democritus.[8]
Corpuscularianism is the postulate, expounded in the 13th-century by the alchemist Pseudo-Geber (Geber),[11]
sometimes identified with Paul of Taranto, that all physical bodies possess an inner and outer layer of minute
particles or corpuscles.[12] Corpuscularianism is similar (this is the electrical pulses ) to the theory atomism, except
that where atoms were supposed to be indivisible, corpuscles could in principle be divided. In this manner, for
example, it was theorized that mercury could penetrate into metals and modify their inner structure.[13]
Corpuscularianism stayed a dominant theory over the next several hundred years.
In 1661, natural philosopher Robert Boyle published The Sceptical Chymist in which he argued that matter was
composed of various combinations of different "corpuscules" or atoms, rather than the classical elements of air,
earth, fire and water.[14] During the 1670s corpuscularianism was used by Isaac Newton in his development of the
corpuscular theory of light.[12] [15]
66
Atom
67
Dalton's atomic hypothesis did not specify the size of atoms. Common
sense indicated they must be very small, but nobody knew how small.
Therefore it was a major landmark when in 1865 Johann Josef Loschmidt measured the size of the molecules that
make up air.
An additional line of reasoning in support of particle theory (and by extension atomic theory) began in 1827 when
botanist Robert Brown used a microscope to look at dust grains floating in water and discovered that they moved
about erraticallya phenomenon that became known as "Brownian motion". J. Desaulx suggested in 1877 that the
phenomenon was caused by the thermal motion of water molecules, and in 1905 Albert Einstein produced the first
mathematical analysis of the motion.[20] [21] [22] French physicist Jean Perrin used Einstein's work to experimentally
determine the mass and dimensions of atoms, thereby conclusively verifying Dalton's atomic theory.[23]
In 1869, building upon earlier discoveries by such scientists as
Lavoisier, Dmitri Mendeleev published the first functional periodic
table.[24] The table itself is a visual representation of the periodic law,
which states that certain chemical properties of elements repeat
periodically when arranged by atomic number.[25]
In 1909, Hans Geiger and Ernest Marsden, under the direction of physicist Ernest Rutherford, bombarded a sheet of
gold foil with alpha raysby then known to be positively charged helium atomsand discovered that a small
percentage of these particles were deflected through much larger angles than was predicted using Thomson's
proposal. Rutherford interpreted the gold foil experiment as suggesting that the positive charge of a heavy gold atom
and most of its mass was concentrated in a nucleus at the center of the atomthe Rutherford model.[27]
Atom
While experimenting with the products of radioactive decay, in 1913 radiochemist Frederick Soddy discovered that
there appeared to be more than one type of atom at each position on the periodic table.[28] The term isotope was
coined by Margaret Todd as a suitable name for different atoms that belong to the same element. J.J. Thomson
created a technique for separating atom types through his work on ionized gases, which subsequently led to the
discovery of stable isotopes.[29]
Meanwhile, in 1913, physicist Niels Bohr suggested that the electrons
were confined into clearly defined, quantized orbits, and could jump
between these, but could not freely spiral inward or outward in
intermediate states.[30] An electron must absorb or emit specific
amounts of energy to transition between these fixed orbits. When the
light from a heated material was passed through a prism, it produced a
multi-colored spectrum. The appearance of fixed lines in this spectrum
was successfully explained by these orbital transitions.[31]
Later in the same year Henry Moseley provided additional
experimental evidence in favor of Niels Bohr's theory. These results
A Bohr model of the hydrogen atom, showing an
refined Ernest Rutherford's and Antonius Van den Broek's model,
electron jumping between fixed orbits and
emitting a photon of energy with a specific
which proposed that the atom contains in its nucleus a number of
frequency.
positive nuclear charges that is equal to its (atomic) number in the
periodic table. Until these experiments, atomic number was not known
to be a physical and experimental quantity. That it is equal to the atomic nuclear charge remains the accepted atomic
model today.[32]
Chemical bonds between atoms were now explained, by Gilbert Newton Lewis in 1916, as the interactions between
their constituent electrons.[33] As the chemical properties of the elements were known to largely repeat themselves
according to the periodic law,[34] in 1919 the American chemist Irving Langmuir suggested that this could be
explained if the electrons in an atom were connected or clustered in some manner. Groups of electrons were thought
to occupy a set of electron shells about the nucleus.[35]
The SternGerlach experiment of 1922 provided further evidence of the quantum nature of the atom. When a beam
of silver atoms was passed through a specially shaped magnetic field, the beam was split based on the direction of an
atom's angular momentum, or spin. As this direction is random, the beam could be expected to spread into a line.
Instead, the beam was split into two parts, depending on whether the atomic spin was oriented up or down.[36]
In 1924, Louis de Broglie proposed that all particles behave to an extent like waves. In 1926, Erwin Schrdinger
used this idea to develop a mathematical model of the atom that described the electrons as three-dimensional
waveforms rather than point particles. A consequence of using waveforms to describe particles is that it is
mathematically impossible to obtain precise values for both the position and momentum of a particle at the same
time; this became known as the uncertainty principle, formulated by Werner Heisenberg in 1926. In this concept, for
a given accuracy in measuring a position one could only obtain a range of probable values for momentum, and vice
versa. This model was able to explain observations of atomic behavior that previous models could not, such as
certain structural and spectral patterns of atoms larger than hydrogen. Thus, the planetary model of the atom was
discarded in favor of one that described atomic orbital zones around the nucleus where a given electron is most likely
to be observed.[37] [38]
68
Atom
69
The development of the mass spectrometer allowed the exact mass of
atoms to be measured. The device uses a magnet to bend the trajectory
of a beam of ions, and the amount of deflection is determined by the
ratio of an atom's mass to its charge. The chemist Francis William
Aston used this instrument to show that isotopes had different masses.
The atomic mass of these isotopes varied by integer amounts, called
the whole number rule.[39] The explanation for these different isotopes
awaited the discovery of the neutron, a neutral-charged particle with a
mass similar to the proton, by the physicist James Chadwick in 1932.
Isotopes were then explained as elements with the same number of
protons, but different numbers of neutrons within the nucleus.[40]
Schematic diagram of a simple mass
spectrometer.
Components
Subatomic particles
Though the word atom originally denoted a particle that cannot be cut into smaller particles, in modern scientific
usage the atom is composed of various subatomic particles. The constituent particles of an atom are the electron, the
proton and the neutron. However, the hydrogen-1 atom has no neutrons and a positive hydrogen ion has no electrons.
The electron is by far the least massive of these particles at 9.111031kg, with a negative electrical charge and a
size that is too small to be measured using available techniques.[47] Protons have a positive charge and a mass 1,836
times that of the electron, at 1.67261027kg, although this can be reduced by changes to the energy binding the
proton into an atom. Neutrons have no electrical charge and have a free mass of 1,839 times the mass of
electrons,[48] or 1.69291027kg. Neutrons and protons have comparable dimensionson the order of
2.51015malthough the 'surface' of these particles is not sharply defined.[49]
In the Standard Model of physics, both protons and neutrons are composed of elementary particles called quarks.
The quark belongs to the fermion group of particles, and is one of the two basic constituents of matterthe other
being the lepton, of which the electron is an example. There are six types of quarks, each having a fractional electric
charge of either +23 or 13. Protons are composed of two up quarks and one down quark, while a neutron consists of
one up quark and two down quarks. This distinction accounts for the difference in mass and charge between the two
particles. The quarks are held together by the strong nuclear force, which is mediated by gluons. The gluon is a
member of the family of gauge bosons, which are elementary particles that mediate physical forces.[50] [51]
Atom
70
Nucleus
The binding energy needed for a nucleon to escape the nucleus, for various isotopes.
All the bound protons and neutrons in an atom make up a tiny atomic nucleus, and are collectively called nucleons.
The radius of a nucleus is approximately equal to
, where A is the total number of nucleons.[52] This is
much smaller than the radius of the atom, which is on the order of 105fm. The nucleons are bound together by a
short-ranged attractive potential called the residual strong force. At distances smaller than 2.5 fm this force is much
more powerful than the electrostatic force that causes positively charged protons to repel each other.[53]
Atoms of the same element have the same number of protons, called the atomic number. Within a single element, the
number of neutrons may vary, determining the isotope of that element. The total number of protons and neutrons
determine the nuclide. The number of neutrons relative to the protons determines the stability of the nucleus, with
certain isotopes undergoing radioactive decay.[54]
The neutron and the proton are different types of fermions. The Pauli exclusion principle is a quantum mechanical
effect that prohibits identical fermions, such as multiple protons, from occupying the same quantum physical state at
the same time. Thus every proton in the nucleus must occupy a different state, with its own energy level, and the
same rule applies to all of the neutrons. This prohibition does not apply to a proton and neutron occupying the same
quantum state.[55]
For atoms with low atomic numbers, a nucleus that has a different number of protons than neutrons can potentially
drop to a lower energy state through a radioactive decay that causes the number of protons and neutrons to more
closely match. As a result, atoms with roughly matching numbers of protons and neutrons are more stable against
decay. However, with increasing atomic number, the mutual repulsion of the protons requires an increasing
proportion of neutrons to maintain the stability of the nucleus, which modifies this trend. Thus, there are no stable
nuclei with equal proton and neutron numbers above atomic number Z = 20 (calcium); and as Z increases toward the
heaviest nuclei, the ratio of neutrons per proton required for stability increases to about 1.5.[55]
Atom
Electron cloud
The electrons in an atom are attracted to the protons in the nucleus by
the electromagnetic force. This force binds the electrons inside an
electrostatic potential well surrounding the smaller nucleus, which
means that an external source of energy is needed for the electron to
escape. The closer an electron is to the nucleus, the greater the
attractive force. Hence electrons bound near the center of the potential
well require more energy to escape than those at greater separations.
Electrons, like other particles, have properties of both a particle and a
A potential well, showing, according to classical
wave. The electron cloud is a region inside the potential well where
mechanics, the minimum energy V(x) needed to
reach
each position x. Classically, a particle with
each electron forms a type of three-dimensional standing wavea
energy E is constrained to a range of positions
wave form that does not move relative to the nucleus. This behavior is
between x1 and x2.
defined by an atomic orbital, a mathematical function that characterises
the probability that an electron appears to be at a particular location
when its position is measured.[61] Only a discrete (or quantized) set of these orbitals exist around the nucleus, as
other possible wave patterns rapidly decay into a more stable form.[62] Orbitals can have one or more ring or node
structures, and they differ from each other in size, shape and orientation.[63]
71
Atom
72
The amount of energy needed to remove or add an electronthe electron binding energyis far less than the
binding energy of nucleons. For example, it requires only 13.6eV to strip a ground-state electron from a hydrogen
atom,[64] compared to 2.23million eV for splitting a deuterium nucleus.[65] Atoms are electrically neutral if they
have an equal number of protons and electrons. Atoms that have either a deficit or a surplus of electrons are called
ions. Electrons that are farthest from the nucleus may be transferred to other nearby atoms or shared between atoms.
By this mechanism, atoms are able to bond into molecules and other types of chemical compounds like ionic and
covalent network crystals.[66]
Properties
Nuclear properties
By definition, any two atoms with an identical number of protons in their nuclei belong to the same chemical
element. Atoms with equal numbers of protons but a different number of neutrons are different isotopes of the same
element. For example, all hydrogen atoms admit exactly one proton, but isotopes exist with no neutrons (hydrogen-1,
by far the most common form,[67] also called protium), one neutron (deuterium), two neutrons (tritium) and more
than two neutrons. The known elements form a set of atomic numbers, from the single proton element hydrogen up
to the 118-proton element ununoctium.[68] All known isotopes of elements with atomic numbers greater than 82 are
radioactive.[69] [70]
About 339 nuclides occur naturally on Earth,[71] of which 255 (about 75%) have not been observed to decay, and are
referred to as "stable isotopes". However, only 90 of these nuclides are stable to all decay, even in theory. Another
165 (bringing the total to 255) have not been observed to decay, even though in theory it is energetically possible.
These are also formally classified as "stable". An additional 33 radioactive nuclides have half-lives longer than 80
million years, and are long-lived enough to be present from the birth of the solar system. This collection of 288
nuclides are known as primordial nuclides. Finally, an additional 51 short-lived nuclides are known to occur
naturally, as daughter products of primordial nuclide decay (such as radium from uranium), or else as products of
natural energetic processes on Earth, such as cosmic ray bombardment (for example, carbon-14).[72] [73]
For 80 of the chemical elements, at least one stable isotope exists. Elements 43, 61, and all elements numbered 83 or
higher have no stable isotopes. As a rule, there is, for each element, only a handful of stable isotopes, the average
being 3.2 stable isotopes per element among those that have stable isotopes. Twenty-six elements have only a single
stable isotope, while the largest number of stable isotopes observed for any element is ten, for the element tin.[74]
Stability of isotopes is affected by the ratio of protons to neutrons, and also by the presence of certain "magic
numbers" of neutrons or protons that represent closed and filled quantum shells. These quantum shells correspond to
a set of energy levels within the shell model of the nucleus; filled shells, such as the filled shell of 50 protons for tin,
confers unusual stability on the nuclide. Of the 255 known stable nuclides, only four have both an odd number of
protons and odd number of neutrons: hydrogen-2 (deuterium), lithium-6, boron-10 and nitrogen-14. Also, only four
naturally occurring, radioactive odd-odd nuclides have a half-life over a billion years: potassium-40, vanadium-50,
lanthanum-138 and tantalum-180m. Most odd-odd nuclei are highly unstable with respect to beta decay, because the
Atom
decay products are even-even, and are therefore more strongly bound, due to nuclear pairing effects.[74]
Mass
The large majority of an atom's mass comes from the protons and neutrons that make it up. The total number of these
particles (called "nucleons") in a given atom is called the mass number. The mass number is a simple whole number,
and has units of "nucleons." An example of use of a mass number is "carbon-12," which has 12 nucleons (six protons
and six neutrons).
The actual mass of an atom at rest is often expressed using the unified atomic mass unit (u), which is also called a
dalton (Da). This unit is defined as a twelfth of the mass of a free neutral atom of carbon-12, which is approximately
1.661027kg.[75] Hydrogen-1, the lightest isotope of hydrogen and the atom with the lowest mass, has an atomic
weight of 1.007825u.[76] The value of this number is called the atomic mass. A given atom has an atomic mass
approximately equal (within 1%) to its mass number times the mass of the atomic mass unit. However, this number
will not be an exact whole number except in the case of carbon-12 (see below)[77] The heaviest stable atom is
lead-208,[69] with a mass of 207.9766521u.[78]
As even the most massive atoms are far too light to work with directly, chemists instead use the unit of moles. The
mole is defined such that one mole of any element always has the same number of atoms (about 6.0221023). This
number was chosen so that if an element has an atomic mass of 1u, a mole of atoms of that element has a mass close
to one gram. Because of the definition of the unified atomic mass unit, each carbon-12 atom has an atomic mass of
exactly 12u, and so a mole of carbon-12 atoms weighs exactly 0.012kg.[75]
73
Atom
Radioactive decay
Every element has one or more isotopes that
have unstable nuclei that are subject to
radioactive decay, causing the nucleus to
emit particles or electromagnetic radiation.
Radioactivity can occur when the radius of a
nucleus is large compared with the radius of
the strong force, which only acts over
distances on the order of 1fm.[88]
The most common forms of radioactive
decay are:[89] [90]
Alpha decay is caused when the nucleus
emits an alpha particle, which is a helium
nucleus consisting of two protons and
two neutrons. The result of the emission
is a new element with a lower atomic
number.
Beta decay is regulated by the weak
force, and results from a transformation
of a neutron into a proton, or a proton
into a neutron. The first is accompanied
by the emission of an electron and an
antineutrino, while the second causes the
This diagram shows the half-life (T) of various isotopes with Z protons and N
emission of a positron and a neutrino.
neutrons.
The electron or positron emissions are
called beta particles. Beta decay either increases or decreases the atomic number of the nucleus by one.
Gamma decay results from a change in the energy level of the nucleus to a lower state, resulting in the emission
of electromagnetic radiation. This can occur following the emission of an alpha or a beta particle from radioactive
decay.
Other more rare types of radioactive decay include ejection of neutrons or protons or clusters of nucleons from a
nucleus, or more than one beta particle, or result (through internal conversion) in production of high-speed electrons
that are not beta rays, and high-energy photons that are not gamma rays.
Each radioactive isotope has a characteristic decay time periodthe half-lifethat is determined by the amount of
time needed for half of a sample to decay. This is an exponential decay process that steadily decreases the proportion
of the remaining isotope by 50% every half-life. Hence after two half-lives have passed only 25% of the isotope is
present, and so forth.[88]
Magnetic moment
Elementary particles possess an intrinsic quantum mechanical property known as spin. This is analogous to the
angular momentum of an object that is spinning around its center of mass, although strictly speaking these particles
are believed to be point-like and cannot be said to be rotating. Spin is measured in units of the reduced Planck
constant (), with electrons, protons and neutrons all having spin , or "spin-". In an atom, electrons in motion
around the nucleus possess orbital angular momentum in addition to their spin, while the nucleus itself possesses
angular momentum due to its nuclear spin.[91]
74
Atom
The magnetic field produced by an atomits magnetic momentis determined by these various forms of angular
momentum, just as a rotating charged object classically produces a magnetic field. However, the most dominant
contribution comes from spin. Due to the nature of electrons to obey the Pauli exclusion principle, in which no two
electrons may be found in the same quantum state, bound electrons pair up with each other, with one member of
each pair in a spin up state and the other in the opposite, spin down state. Thus these spins cancel each other out,
reducing the total magnetic dipole moment to zero in some atoms with even number of electrons.[92]
In ferromagnetic elements such as iron, an odd number of electrons leads to an unpaired electron and a net overall
magnetic moment. The orbitals of neighboring atoms overlap and a lower energy state is achieved when the spins of
unpaired electrons are aligned with each other, a process known as an exchange interaction. When the magnetic
moments of ferromagnetic atoms are lined up, the material can produce a measurable macroscopic field.
Paramagnetic materials have atoms with magnetic moments that line up in random directions when no magnetic field
is present, but the magnetic moments of the individual atoms line up in the presence of a field.[92] [93]
The nucleus of an atom can also have a net spin. Normally these nuclei are aligned in random directions because of
thermal equilibrium. However, for certain elements (such as xenon-129) it is possible to polarize a significant
proportion of the nuclear spin states so that they are aligned in the same directiona condition called
hyperpolarization. This has important applications in magnetic resonance imaging.[94] [95]
Energy levels
When an electron is bound to an atom, it has a potential energy that is inversely proportional to its distance from the
nucleus. This is measured by the amount of energy needed to unbind the electron from the atom, and is usually given
in units of electronvolts (eV). In the quantum mechanical model, a bound electron can only occupy a set of states
centered on the nucleus, and each state corresponds to a specific energy level. The lowest energy state of a bound
electron is called the ground state, while an electron at a higher energy level is in an excited state.[96]
For an electron to transition between two different states, it must absorb or emit a photon at an energy matching the
difference in the potential energy of those levels. The energy of an emitted photon is proportional to its frequency, so
these specific energy levels appear as distinct bands in the electromagnetic spectrum.[97] Each element has a
characteristic spectrum that can depend on the nuclear charge, subshells filled by electrons, the electromagnetic
interactions between the electrons and other factors.[98]
When a continuous spectrum of energy is
passed through a gas or plasma, some of the
photons are absorbed by atoms, causing
electrons to change their energy level. Those
excited electrons that remain bound to their
atom spontaneously emit this energy as a
An example of absorption lines in a spectrum.
photon, traveling in a random direction, and
so drop back to lower energy levels. Thus
the atoms behave like a filter that forms a series of dark absorption bands in the energy output. (An observer viewing
the atoms from a view that does not include the continuous spectrum in the background, instead sees a series of
emission lines from the photons emitted by the atoms.) Spectroscopic measurements of the strength and width of
spectral lines allow the composition and physical properties of a substance to be determined.[99]
Close examination of the spectral lines reveals that some display a fine structure splitting. This occurs because of
spin-orbit coupling, which is an interaction between the spin and motion of the outermost electron.[100] When an
atom is in an external magnetic field, spectral lines become split into three or more components; a phenomenon
called the Zeeman effect. This is caused by the interaction of the magnetic field with the magnetic moment of the
atom and its electrons. Some atoms can have multiple electron configurations with the same energy level, which thus
appear as a single spectral line. The interaction of the magnetic field with the atom shifts these electron
75
Atom
76
configurations to slightly different energy levels, resulting in multiple spectral lines.[101] The presence of an external
electric field can cause a comparable splitting and shifting of spectral lines by modifying the electron energy levels, a
phenomenon called the Stark effect.[102]
If a bound electron is in an excited state, an interacting photon with the proper energy can cause stimulated emission
of a photon with a matching energy level. For this to occur, the electron must drop to a lower energy state that has an
energy difference matching the energy of the interacting photon. The emitted photon and the interacting photon then
move off in parallel and with matching phases. That is, the wave patterns of the two photons are synchronized. This
physical property is used to make lasers, which can emit a coherent beam of light energy in a narrow frequency
band.[103]
States
Quantities of atoms are found in different states of matter that depend
on the physical conditions, such as temperature and pressure. By
varying the conditions, materials can transition between solids, liquids,
gases and plasmas. [108] Within a state, a material can also exist in
different phases. An example of this is solid carbon, which can exist as
graphite or diamond.[109]
At temperatures close to absolute zero, atoms can form a
BoseEinstein condensate, at which point quantum mechanical effects,
Snapshots illustrating the formation of a
which are normally only observed at the atomic scale, become apparent
BoseEinstein condensate.
on a macroscopic scale.[110] [111] This super-cooled collection of atoms
then behaves as a single super atom, which may allow fundamental checks of quantum mechanical behavior.[112]
Atom
77
Identification
The scanning tunneling microscope is a device for viewing surfaces at
the atomic level. It uses the quantum tunneling phenomenon, which
allows particles to pass through a barrier that would normally be
insurmountable. Electrons tunnel through the vacuum between two
planar metal electrodes, on each of which is an adsorbed atom,
providing a tunneling-current density that can be measured. Scanning
one atom (taken as the tip) as it moves past the other (the sample)
permits plotting of tip displacement versus lateral separation for a
constant current. The calculation shows the extent to which
scanning-tunneling-microscope images of an individual atom are
visible. It confirms that for low bias, the microscope images the
space-averaged dimensions of the electron orbitals across closely
packed energy levelsthe Fermi level local density of states.[113] [114]
Atom
Nucleosynthesis
Stable protons and electrons appeared one second after the Big Bang. During the following three minutes, Big Bang
nucleosynthesis produced most of the helium, lithium, and deuterium in the universe, and perhaps some of the
beryllium and boron.[124] [125] [126] The first atoms (complete with bound electrons) were theoretically created
380,000years after the Big Bangan epoch called recombination, when the expanding universe cooled enough to
allow electrons to become attached to nuclei.[127]
Since the Big Bang, which produced no carbon, atomic nuclei have been combined in stars through the process of
nuclear fusion to produce more of the element helium, and (via the triple alpha process) the sequence of elements
from carbon up to iron.[128]
Isotopes such as lithium-6, as well as some beryllium and boron are generated in space through cosmic ray
spallation.[129] This occurs when a high-energy proton strikes an atomic nucleus, causing large numbers of nucleons
to be ejected.
Elements heavier than iron were produced in supernovae through the r-process and in AGB stars through the
s-process, both of which involve the capture of neutrons by atomic nuclei.[130] Elements such as lead formed largely
through the radioactive decay of heavier elements.[131]
Earth
Most of the atoms that make up the Earth and its inhabitants were present in their current form in the nebula that
collapsed out of a molecular cloud to form the Solar System. The rest are the result of radioactive decay, and their
relative proportion can be used to determine the age of the Earth through radiometric dating.[132] [133] Most of the
helium in the crust of the Earth (about 99% of the helium from gas wells, as shown by its lower abundance of
helium-3) is a product of alpha decay.[134]
There are a few trace atoms on Earth that were not present at the beginning (i.e., not "primordial"), nor are results of
radioactive decay. Carbon-14 is continuously generated by cosmic rays in the atmosphere.[135] Some atoms on Earth
have been artificially generated either deliberately or as by-products of nuclear reactors or explosions.[136] [137] Of
the transuranic elementsthose with atomic numbers greater than 92only plutonium and neptunium occur
naturally on Earth.[138] [139] Transuranic elements have radioactive lifetimes shorter than the current age of the
Earth[140] and thus identifiable quantities of these elements have long since decayed, with the exception of traces of
plutonium-244 possibly deposited by cosmic dust.[132] Natural deposits of plutonium and neptunium are produced by
neutron capture in uranium ore.[141]
The Earth contains approximately 1.331050 atoms.[142] In the planet's atmosphere, small numbers of independent
atoms of noble gases exist, such as argon and neon. The remaining 99% of the atmosphere is bound in the form of
molecules, including carbon dioxide and diatomic oxygen and nitrogen. At the surface of the Earth, atoms combine
to form various compounds, including water, salt, silicates and oxides. Atoms can also combine to create materials
that do not consist of discrete molecules, including crystals and liquid or solid metals.[143] [144] This atomic matter
forms networked arrangements that lack the particular type of small-scale interrupted order associated with
molecular matter.[145]
78
Atom
79
Notes
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[137] Diamond, H; et al. (1960). "Heavy Isotope Abundances in Mike Thermonuclear Device". Physical Review 119 (6): 200004.
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[139] Keller, C. (1973). "Natural occurrence of lanthanides, actinides, and superheavy elements". Chemiker Zeitung 97 (10): 52230.
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[140] Zaider & Rossi 2001, p.17.
[141] "Oklo Fossil Reactors" (http:/ / www. oklo. curtin. edu. au/ index. cfm). Curtin University of Technology. . Retrieved 2008-01-15.
[142] Weisenberger, Drew. "How many atoms are there in the world?" (http:/ / education. jlab. org/ qa/ mathatom_05. html). Jefferson Lab. .
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[143] Pidwirny, Michael. "Fundamentals of Physical Geography" (http:/ / www. physicalgeography. net/ fundamentals/ contents. html).
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[144] Anderson, Don L. (2002). "The inner inner core of Earth". Proceedings of the National Academy of Sciences 99 (22): 1396668.
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[145] Pauling 1960, pp.510.
[146] Anonymous (October 2, 2001). "Second postcard from the island of stability" (http:/ / cerncourier. com/ cws/ article/ cern/ 28509). CERN
Courier. . Retrieved 2008-01-14.
[147] Jacoby, Mitch (2006). "As-yet-unsynthesized superheavy atom should form a stable diatomic molecule with fluorine". Chemical &
Engineering News 84 (10): 19.
[148] Koppes, Steve (March 1, 1999). "Fermilab Physicists Find New Matter-Antimatter Asymmetry" (http:/ / www-news. uchicago. edu/
releases/ 99/ 990301. ktev. shtml). University of Chicago. . Retrieved 2008-01-14.
[149] Cromie, William J. (August 16, 2001). "A lifetime of trillionths of a second: Scientists explore antimatter" (http:/ / news. harvard. edu/
gazette/ 2001/ 08. 16/ antimatter. html). Harvard University Gazette. . Retrieved 2008-01-14.
[150] Hijmans, Tom W. (2002). "Particle physics: Cold antihydrogen". Nature 419 (6906): 43940. doi:10.1038/419439a. PMID12368837.
[151] Staff (October 30, 2002). "Researchers 'look inside' antimatter" (http:/ / news. bbc. co. uk/ 2/ hi/ science/ nature/ 2375717. stm). BBC
News. . Retrieved 2008-01-14.
Atom
84
[152] Barrett, Roger (1990). "The Strange World of the Exotic Atom" (http:/ / media. newscientist. com/ article/ mg12717284.
600-the-strange-world-of-the-exotic-atom-physicists-can-nowmake-atoms-and-molecules-containing-negative-particles-other-than-electronsand-use-them-not-just
html). New Scientist (1728): 77115. . Retrieved 2008-01-04.
[153] Indelicato, Paul (2004). "Exotic Atoms". Physica Scripta T112 (1): 2026. arXiv:physics/0409058. Bibcode2004PhST..112...20I.
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[154] Ripin, Barrett H. (July 1998). "Recent Experiments on Exotic Atoms" (http:/ / www. aps. org/ publications/ apsnews/ 199807/ experiment.
cfm. html). American Physical Society. . Retrieved 2008-02-15.
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Choppin, Gregory R.; Liljenzin, Jan-Olov; Rydberg, Jan (2001). Radiochemistry and Nuclear Chemistry.
Elsevier. ISBN0-7506-7463-6. OCLC162592180.
Dalton, J. (1808). A New System of Chemical Philosophy, Part 1. London and Manchester: S. Russell.
Demtrder, Wolfgang (2002). Atoms, Molecules and Photons: An Introduction to Atomic- Molecular- and
Quantum Physics (1st ed.). Springer. ISBN3-540-20631-0. OCLC181435713.
Feynman, Richard (1995). Six Easy Pieces. The Penguin Group. ISBN978-0-14-027666-4. OCLC40499574.
Fowles, Grant R. (1989). Introduction to Modern Optics. Courier Dover Publications. ISBN0-486-65957-7.
OCLC18834711.
Gangopadhyaya, Mrinalkanti (1981). Indian Atomism: History and Sources. Atlantic Highlands, New Jersey:
Humanities Press. ISBN0-391-02177-X. OCLC10916778.
Goodstein, David L. (2002). States of Matter. Courier Dover Publications. ISBN0-13-843557-X.
Harrison, Edward Robert (2003). Masks of the Universe: Changing Ideas on the Nature of the Cosmos.
Cambridge University Press. ISBN0-521-77351-2. OCLC50441595.
Iannone, A. Pablo (2001). Dictionary of World Philosophy. Routledge. ISBN0-415-17995-5. OCLC44541769.
Jevremovic, Tatjana (2005). Nuclear Principles in Engineering. Springer. ISBN0-387-23284-2.
OCLC228384008.
King, Richard (1999). Indian philosophy: an introduction to Hindu and Buddhist thought. Edinburgh University
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Lequeux, James (2005). The Interstellar Medium. Springer. ISBN3-540-21326-0. OCLC133157789.
Levere, Trevor, H. (2001). Transforming Matter A History of Chemistry for Alchemy to the Buckyball. The
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85
Atom
External links
Francis, Eden (2002). "Atomic Size" (http://dl.clackamas.cc.or.us/ch104-07/atomic_size.htm). Clackamas
Community College. Retrieved 2007-01-09.
Freudenrich, Craig C.. "How Atoms Work" (http://www.howstuffworks.com/atom.htm). How Stuff Works.
Retrieved 2007-01-09.
"The Atom" (http://en.wikibooks.org/wiki/FHSST_Physics/Atom). Free High School Science Texts: Physics.
Wikibooks. Retrieved 2010-07-10.
Anonymous (2007). "The atom" (http://www.scienceaid.co.uk/chemistry/fundamental/atom.html). Science
aid+. Retrieved 2010-07-10.a guide to the atom for teens.
Anonymous (2006-01-03). "Atoms and Atomic Structure" (http://www.bbc.co.uk/dna/h2g2/A6672963).
BBC. Retrieved 2007-01-11.
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pl?Type=TOC). University of Colorado. Retrieved 2008-01-11.
Various (2006-02-03). "What does an atom look like?" (http://www.hydrogenlab.de/elektronium/HTML/
einleitung_hauptseite_uk.html). University of Karlsruhe. Retrieved 2008-05-12.
Atomic nucleus
86
Atomic nucleus
87
A figurative depiction of the helium-4 atom with the electron cloud in shades of
gray. In the nucleus, the two protons and two neutrons are depicted in red and blue.
This depiction shows the particles as separate, whereas in an actual helium atom,
the protons are superimposed in space and most likely found at the very center of
the nucleus, and the same is true of the two neutrons. Thus, all four particles are
most likely found in exactly the same space, at the central point. Classical images
of separate particles fail to model known charge distributions in very small nuclei.
A more accurate image is that the spacial distribution of nucleons in helium's
nucleus, although on a far smaller scale, is much closer to the helium electron
cloud shown here, than to the fanciful nucleus image
Introduction
Etymology
The term nucleus is from the Latin word nucleus , a diminutive of nux ("nut"), meaning the kernel (i.e., the "small
nut") inside a fruit. In 1844, Michael Faraday used the term to refer to the "central point of an atom". The modern
atomic meaning was proposed by Ernest Rutherford in 1912.[2] The adoption of the term "nucleus" to atomic theory,
however, was not immediate. In 1916, for example, Gilbert N. Lewis stated, in his famous article The Atom and the
Molecule, that "the atom is composed of the kernel and an outer atom or shell"[3]
Nuclear makeup
The nucleus of an atom consists of protons and neutrons (two types of baryons) bound by the nuclear force (also
known as the residual strong force). These baryons are further composed of subatomic fundamental particles
known as quarks bound by the strong interaction. Which chemical element an atom represents is determined by the
number of protons in the nucleus. Each proton carries a single positive charge, and the total electrical charge of the
nucleus is spread fairly uniformly throughout its body, with a fall-off at the edge.
Atomic nucleus
Major exceptions to this rule are the light elements hydrogen and helium, where the charge is concentrated most
highly at the single central point (without a central volume of uniform charge). This configuration is the same as for
1s electrons in atomic orbitals, and is the expected density distribution for fermions (in this case, protons) in 1s states
without orbital angular momentum.[4]
As each proton carries a unit of charge, the charge distribution is indicative of the proton distribution. The neutron
distribution probably is similar.[4]
Forces
Nuclei are bound together by the residual strong force (nuclear force). The residual strong force is minor residuum of
the strong interaction which binds quarks together to form protons and neutrons. This force is much weaker between
neutrons and protons because it is mostly neutralized within them, in the same way that electromagnetic forces
between neutral atoms (such as van der Waals forces that act between two inert gas atoms) are much weaker than the
electromagnetic forces that hold the parts of the atoms internally together (for example, the forces that hold the
electrons in an inert gas atom bound to its nucleus).
The nuclear force is highly attractive at the distance of typical nucleon separation, and this overwhelms the repulsion
between protons which is due to the electromagnetic force, thus allowing nuclei to exist. However, because the
residual strong force has a limited range because it decays quickly with distance (see Yukawa potential), only nuclei
smaller than a certain size can be completely stable. The largest known completely stable (e.g., stable to alpha, beta,
and gamma decay) nucleus is lead-208 which contains a total of 208 nucleons (126 neutrons and 82 protons). Nuclei
larger than this maximal size of 208 particles are unstable and (as a trend) become increasingly short-lived with
larger size, as the number of neutrons and protons which compose them increases beyond this number. However,
bismuth-209 is also stable to beta decay and has the longest half-life to alpha decay of any known isotope, estimated
at a billion times longer than the age of the universe.
The residual strong force is effective over a very short range (usually only a few fermis; roughly one or two nucleon
diameters) and causes an attraction between any pair of nucleons. For example, between protons and neutrons to
form [NP] deuteron, and also between protons and protons, and neutrons and neutrons.
88
Atomic nucleus
Nuclear models
There are many different historical models of the atomic nucleus, none of which to this day completely explains
experimental data on nuclear structure.[8]
The nuclear radius (R) is considered to be one of the basic things that any model must predict. For stable nuclei (not
halo nuclei or other unstable distorted nuclei) the nuclear radius is roughly proportional to the cube root of the mass
number (A) of the nucleus, and particularly in nuclei containing many nucleons, as they arrange in more spherical
configurations:
The stable nucleus has approximately a constant density and therefore the nuclear radius R can be approximated by
the following formula,
where A = Atomic mass number (the number of protons, Z, plus the number of neutrons, N) and
r0=1.25fm=1.251015m. In this equation, the constant r0 varies by 0.2fm, depending on the nucleus in
question, but this is less than 20% change from a constant.[9]
In other words, packing protons and neutrons in the nucleus gives approximately the same total size result as packing
hard spheres of a constant size (like marbles) into a tight spherical or semi-spherical bag (some stable nuclei are not
quite spherical, but are known to be prolate).
89
Atomic nucleus
90
Atomic nucleus
Notes
[1] Geoff Brumfiel (July 7, 2010). "The proton shrinks in size". Nature. doi:10.1038/news.2010.337.
[2] D. Harper. "Nucleus" (http:/ / www. etymonline. com/ index. php?search=Nucleus& searchmode=none). Online Etymology Dictionary. .
Retrieved 2010-03-06.
[3] G.N. Lewis (1916). "The Atom and the Molecule" (http:/ / osulibrary. oregonstate. edu/ specialcollections/ coll/ pauling/ bond/ papers/
corr216. 3-lewispub-19160400. html). Journal of the American Chemical Society 38 (4): 4. doi:10.1021/ja02261a002. .
[4] J.-L. Basdevant, J. Rich, M. Spiro (2005). Fundamentals in Nuclear Physics (http:/ / books. google. com/ ?id=OFx7P9mgC9oC&
pg=PA375& dq=helium+ "nuclear+ structure"). Springer. p.13, Fig. 1.1. ISBN0387016724. .
[5] A.G. Sitenko, V.K. Tartakovski (1997). Theory of Nucleus: Nuclear Structure and Nuclear Interaction (http:/ / books. google. com/
?id=swb9QpqOqtAC& pg=PA464& dq=isbn=0792344235#PPA3,M1). Kluwer Academic. p.3. ISBN0792344235. .
[6] M.A. Srednicki (2007). Quantum Field Theory. Cambridge University Press. pp.522523. ISBN9780521864497.
[7] J.-L. Basdevant, J. Rich, M. Spiro (2005). Fundamentals in Nuclear Physics (http:/ / books. google. com/ ?id=OFx7P9mgC9oC&
pg=PA375& dq=helium+ "nuclear+ structure"). Springer. p.155. ISBN0387016724. .
[8] N.D. Cook (2010). Models of the Atomic Nucleus (2nd ed.). Springer. p.57 ff.. ISBN978-3-642-14736-4.
[9] K.S. Krane (1987). Introductory Nuclear Physics. Wiley-VCH. ISBN0-471-80553-X.
References
N.D. Cook (2010). Models of the Atomic Nucleus (2nd ed.). Springer. ISBN978-3-642-14736-4.
External links
The Nucleus - a chapter from an online textbook (http://www.lightandmatter.com/html_books/4em/ch02/
ch02.html)
The LIVEChart of Nuclides - IAEA (http://www-nds.iaea.org/livechart) in Java (http://www-nds.iaea.org/
livechart) or HTML (http://www-nds.iaea.org/relnsd/vcharthtml/VChartHTML.html)
Article on the "nuclear shell model," giving nuclear shell filling for the various elements (http://www.
halexandria.org/dward472.htm). Accessed Sept. 16, 2009.
91
Proton
92
Proton
Proton
The quark structure of the proton. (The color assignment of individual quarks is not important, only that all three colors are present.)
Classification
Baryon
Composition
Statistics
Fermionic
Interactions
Symbol
p, p+, N+
Antiparticle
Antiproton
Theorized
Discovered
Mass
1.672621777(74)1027kg
[1]
938.272046(21)MeV/c2
[1]
1.007276466812(90)u
Mean lifetime
>2.11029yr (stable)
Electric charge
1e
[1]
1.602176565(35)1019C
Charge radius
0.8775(51)fm
<5.41024ecm
Electric polarizability
1.20(6)103fm3
Magnetic moment
1.410606743(33)1026JT1
[1]
1.521032210(12)103B
[1]
2.792847356(23)N
Magnetic polarizability
1.9(5)104fm3
Spin
Isospin
Parity
+1
Condensed
I(JP) = 12(12+)
[1]
[1]
[1]
2
2
Proton
93
The proton is a subatomic particle with the symbol p or p+ and a positive electric charge of 1 elementary charge.
One or more protons are present in the nucleus of each atom, along with neutrons. The number of protons in each
atom is its atomic number.
In the standard model of particle physics, the proton is a hadron, composed of quarks. Prior to that model becoming a
consensus in the physics community, the proton was considered a fundamental particle. A proton is composed of two
up quarks and one down quark, and is about 1.61.7fm in diameter.[2]
The free proton is stable and is found naturally in a number of situations. Free protons exist in plasmas in which
temperatures are too high to allow them to combine with electrons. Free protons of high energy and velocity make
up 90% of cosmic rays, which propagate in vacuum for interstellar distances. Free protons are emitted directly from
atomic nuclei in some rare types of radioactive decay, and also result from the decay of free neutrons, which are
unstable. In all such cases, protons must lose sufficient velocity and (kinetic energy) to allow them to become
associated with electrons, since this is a relatively low-energy interaction. However, in such an association, the
character of the bound proton is not changed, and it remains a proton.
The attraction of low-energy protons to electrons, either free electrons or electrons as present in normal matter,
causes such protons to soon form chemical bonds with atoms. This happens at sufficiently "cold" temperatures
(comparable to temperatures at the surface of the Sun). In interaction with normal (non plasma) matter, low-velocity
free protons are attracted to electrons in any atom or molecule with which they come in contact, causing them to
combine. In vacuum, a sufficiently slow proton may pick up a free electron, becoming a neutral hydrogen atom,
which then will then react chemically with other atoms if they are available and sufficiently cold.
Description
Protons are spin- fermions and are composed of three quarks,[3] making them baryons (a sub-type of hadrons). The
two up quarks and one down quark of the proton are held together by the strong force, mediated by gluons.[2] The
proton has an approximately exponentially decaying positive charge distribution with a mean square radius of about
0.8 fm.[4]
Protons and neutrons are both nucleons, which may be bound by the nuclear force into atomic nuclei. The nucleus of
the most common isotope of the hydrogen atom (with the chemical symbol "H") is a lone proton. The nuclei of the
heavy hydrogen isotopes deuterium and tritium contain one proton bound to one and two neutrons, respectively. All
other types of atoms are composed of two or more protons and various numbers of neutrons.
Stability
The spontaneous decay of free protons has never been observed, and the proton is therefore considered a stable
particle. However, some grand unified theories of particle physics predict that proton decay should take place with
lifetimes of the order of 1036yr, and experimental searches have established lower bounds on the mean lifetime of
the proton for various assumed decay products.
Experiments at the Super-Kamiokande detector in Japan gave lower limits for proton mean lifetime of 6.61033yr
for decay to an antimuon and a neutral pion, and 8.21033yr for decay to a positron and a neutral pion.[5] Another
experiment at the Sudbury Neutrino Observatory in Canada searched for gamma rays resulting from residual nuclei
resulting from the decay of a proton from oxygen-16. This experiment was designed to detect decay to any product,
and established a lower limit to the proton lifetime of 2.11029yr.[6]
However, protons are known to transform into neutrons through the process of electron capture (also called inverse
beta decay). For free protons, this process does not occur spontaneously but only when energy is supplied. The
equation is:
p+ + e n + e
Proton
The process is reversible; neutrons can convert back to protons through beta decay, a common form of radioactive
decay. In fact, a free neutron decays this way, with a mean lifetime of about 15 minutes.
Charge radius
The internationally-accepted value of the proton's charge radius is 0.8768fm (see orders of magnitude for
comparison to other sizes). This value is based on measurements involving a proton and an electron.
However, since July 5, 2010, an international research team has been able to make measurements involving a proton
and a negatively-charged muon. After a long and careful analysis of those measurements, the team concluded that
the root-mean-square charge radius of a proton is "0.84184(67)fm, which differs by 5.0 standard deviations from the
CODATA value of 0.8768(69)fm."[11]
The international research team that obtained this result at the Paul-Scherrer-Institut (PSI) in Villigen (Switzerland)
includes scientists from the Max Planck Institute of Quantum Optics (MPQ) in Garching, the
Ludwig-Maximilians-Universitt (LMU) Munich and the Institut fr Strahlwerkzeuge (IFWS) of the Universitt
Stuttgart (both from Germany), and the University of Coimbra, Portugal.[12] [13] They are now attempting to explain
the discrepancy, and re-examining the results of both previous high-precision measurements and complicated
calculations. If no errors are found in the measurements or calculations, it could be necessary to re-examine the
worlds most precise and best-tested fundamental theory: quantum electrodynamics.[14]
94
Proton
Proton in chemistry
Atomic number
In chemistry, the number of protons in the nucleus of an atom is known as the atomic number, which determines the
chemical element to which the atom belongs. For example, the atomic number of chlorine is 17; this means that each
chlorine atom has 17 protons and that all atoms with 17 protons are chlorine atoms. The chemical properties of each
atom are determined by the number of (negatively charged) electrons, which for neutral atoms is equal to the number
of (positive) protons so that the total charge is zero. For example, a neutral chlorine atom has 17 protons and 17
electrons, whereas a negative Cl ion has 17 protons and 18 electrons for a total charge of 1.
All atoms of a given element are not necessarily identical, however, as the number of neutrons may vary to form
different isotopes, and energy levels may differ forming different nuclear isomers. For example, there are two stable
isotopes of chlorine: Cl with 35 - 17 = 18 neutrons and Cl with 37 - 17 = 20 neutrons.
Hydrogen ion
In chemistry, the term proton refers to the hydrogen ion, H+. Since the atomic number of hydrogen is 1, a hydrogen
ion has no electrons and corresponds to a bare nucleus, consisting of a proton (and 0 neutrons for the most abundant
isotope protium H). The proton is a "bare charge" with only about 1/64,000th of the radius of a hydrogen atom, and
so is extremely reactive chemically. The free proton thus has an extremely short lifetime in chemical systems such as
liquids and it reacts immediately with the electron cloud of any available molecule. In aqueous solution, it forms the
hydronium ion, which in turn is further solvated by water molecules in clusters such as [H5O2]+ and [H9O4]+.[15]
The transfer of H+ in an acidbase reaction is usually referred to as "proton transfer". The acid is referred to as a
proton donor and the base as a proton acceptor. Likewise, biochemical terms such as proton pump and proton
channel refer to the movement of hydrated H+ ions.
The ion produced by removing the electron from a deuterium atom, is known as a deuteron, not a proton. Similarly,
removing an electron from a tritium atom produces a triton.
History
The concept of a hydrogen-like particle as a constituent of other atoms was developed over a long period. As early as
1815, William Prout proposed that all atoms are composed of hydrogen atoms, based on a simplistic interpretation of
early values of atomic weights (see Prout's hypothesis), which was disproved when more accurate values were
measured.
In 1886, Eugen Goldstein discovered canal rays (also known as anode rays) and showed that they were positively
charged particles (ions) produced from gases. However, since particles from different gases had different values of
charge-to-mass ratio (e/m), they could not be identified with a single particle, unlike the negative electrons
discovered by J. J. Thomson.
Following the discovery of the atomic nucleus by Ernest Rutherford in 1911, Antonius van den Broek proposed that
the place of each element in the periodic table (its atomic number) is equal to its nuclear charge. This was confirmed
experimentally by Henry Moseley in 1913 using X-ray spectra. In 1917, (in experiments reported in 1919)
Rutherford proved that the hydrogen nucleus is present in other nuclei, a result usually described as the discovery of
95
Proton
96
the proton.[16] He noticed that, when alpha particles were shot into air, and (after experimentation) to a higher degree
into pure nitrogen gas, his scintillation detectors showed the signatures of hydrogen nuclei. Rutherford determined
that this hydrogen could have come only from the nitrogen, and therefore nitrogen must contain hydrogen nuclei.
One hydrogen nucleus was being knocked off by the impact of the alpha particle, producing oxygen-17 in the
process. This was the first reported nuclear reaction, 14N + 17O + p. The hydrogen nucleus is, therefore, present
in other nuclei as an elementary particle, which Rutherford named the proton, after the neuter singular of the Greek
word for "first", .
Exposure
The Apollo Lunar Surface Experiments Packages (ALSEP) determined that more than 95% of the particles in the
solar wind are electrons and protons, in approximately equal numbers.[17] [18]
Because the Solar Wind Spectrometer made continuous measurements, it was possible to measure how
the Earth's magnetic field affects arriving solar wind particles. For about two-thirds of each orbit, the
Moon is outside of the Earth's magnetic field. At these times, a typical proton density was 10 to 20 per
cubic centimeter, with most protons having velocities between 400 and 650 kilometers per second. For
about five days of each month, the Moon is inside the Earth's geomagnetic tail, and typically no solar
wind particles were detectable. For the remainder of each lunar orbit, the Moon is in a transitional region
known as the magnetosheath, where the Earth's magnetic field affects the solar wind but does not
completely exclude it. In this region, the particle flux is reduced, with typical proton velocities of 250 to
450 kilometers per second. During the lunar night, the spectrometer was shielded from the solar wind by
the Moon and no solar wind particles were measured.[17]
Research has been performed on the dose-rate effects of protons, as typically found in space travel, on human
health.[18] [19] To be more specific, there are hopes to identify what specific chromosomes are damaged, and to
define the damage, during cancer development from proton exposure.[18] Another study looks into determining "the
effects of exposure to proton irradiation on neurochemical and behavioral endpoints, including dopaminergic
functioning, amphetamine-induced conditioned taste aversion learning, and spatial learning and memory as
measured by the Morris water maze."[19] Electrical charging of a spacecraft due to interplanetary proton
bombardment has also been proposed for study.[20] There are many more studies that pertain to space travel,
including galactic cosmic rays and their possible health effects, and solar proton event exposure.
The American Biostack and Soviet Biorack space travel experiments have demonstrated the severity of molecular
damage induced by heavy ions on micro organisms including Artemia cysts.[21]
Antiproton
CPT-symmetry puts strong constraints on the relative properties of particles and antiparticles and, therefore, is open
to stringent tests. For example, the charges of the proton and antiproton must sum to exactly zero. This equality has
been tested to one part in 108. The equality of their masses has also been tested to better than one part in 108.
By holding antiprotons in a Penning trap, the equality of the charge to mass ratio of the proton and the antiproton has
been tested to one part in 6109.[22] The magnetic moment of the antiproton has been measured with error of
8103 nuclear Bohr magnetons, and is found to be equal and opposite to that of the proton.
Proton
References
[1] P.J. Mohr, B.N. Taylor, and D.B. Newell (2011), "The 2010 CODATA Recommended Values of the Fundamental Physical Constants" (Web
Version 6.0). This database was developed by J. Baker, M. Douma, and S. Kotochigova. Available: http:/ / physics. nist. gov/ constants
[Thursday, 02-Jun-2011 21:00:12 EDT]. National Institute of Standards and Technology, Gaithersburg, MD 20899.
[2] W.N. Cottingham, D.A. Greenwood (1986). An Introduction to Nuclear Physics. Cambridge University Press. p.19.
[3] R.K. Adair (1989). The Great Design: Particles, Fields, and Creation. Oxford University Press. p.214.
[4] J.-L. Basdevant, J. Rich, M. Spiro (2005). Fundamentals in Nuclear Physics (http:/ / books. google. com/ ?id=OFx7P9mgC9oC&
pg=PA375& dq=helium+ "nuclear+ structure"). Springer. p.155. ISBN0-387-01672-4. .
[5] H. Nishino et al. (Kamiokande collaboration) (2009). "Search for Proton Decay via p e+ 0 and p + 0 in a Large Water Cherenkov
Detector". Physical Review Letters 102: 141801. Bibcode2009PhRvL.102n1801N. doi:10.1103/PhysRevLett.102.141801.
[6] S.N. Ahmed et al. (SNO Collaboration) (2004). "Constraints on nucleon decay via invisible modes from the Sudbury Neutrino Observatory".
Physical Review Letters 92: 102004. arXiv:hep-ex/0310030. Bibcode2004PhRvL..92j2004A. doi:10.1103/PhysRevLett.92.102004.
PMID15089201.
[7] See this news report (http:/ / www. sciencenews. org/ view/ generic/ id/ 38788/ title/
Standard_model_gets_right_answer_for_proton,_neutron_masses) and links
[8] S. Drr, Z. Fodor, J. Frison, C. Hoelbling, R. Hoffmann, S. D. Katz, S. Krieg, T. Kurth, L. Lellouch, T. Lippert, K. K. Szabo, and G. Vulvert
(21 November 2008). "Ab Initio Determination of Light Hadron Masses" (http:/ / www. sciencemag. org/ cgi/ data/ 322/ 5905/ 1224/ DC1/ 1).
Science 322 (5905): 1224. Bibcode2008Sci...322.1224D. doi:10.1126/science.1163233. PMID19023076. .
[9] C. F. Perdrisat, V. Punjabi, M. Vanderhaeghen (2007). "Nucleon Electromagnetic Form Factors". Prog Part Nucl Phys 59: 694764.
arXiv:hep-ph/0612014. Bibcode2007PrPNP..59..694P. doi:10.1016/j.ppnp.2007.05.001.
[10] Sigfrido Boffi & Barbara Pasquini (2007). "Generalized parton distributions and the structure of the nucleon". Riv Nuovo Cim 30.
arXiv:0711.2625. Bibcode2007NCimR..30..387B. doi:10.1393/ncr/i2007-10025-7.
[11] Randolf Pohl, Aldo Antognini, Franois Nez, Fernando D. Amaro, Franois Biraben, Joo M. R. Cardoso, Daniel S. Covita, Andreas Dax,
Satish Dhawan, Luis M. P. Fernandes, Adolf Giesen, Thomas Graf, Theodor W. Hnsch, Paul Indelicato, Lucile Julien, Cheng-Yang Kao,
Paul Knowles, Eric-Olivier Le Bigot, Yi-Wei Liu, Jos A. M. Lopes, Livia Ludhova, Cristina M. B. Monteiro, Franoise Mulhauser, Tobias
Nebel, Paul Rabinowitz, et al. (8 July 2010). "The size of the proton" (http:/ / www. nature. com/ nature/ journal/ v466/ n7303/ abs/
nature09250. html). Nature 466 (7303): 213216. Bibcode2010Natur.466..213P. doi:10.1038/nature09250. PMID20613837. . Retrieved
2010-07-09.
[12] New proton measurements may throw physics a curve (http:/ / www. azonano. com/ news. asp?newsID=18428)
[13] "The Proton Just Got Smaller" (http:/ / www. photonics. com/ Article. aspx?AID=42905). Photonics.Com. July 12, 2010. . Retrieved
2010-07-19.
[14] Researchers Observes Unexpectedly Small Proton Radius in a Precision Experiment (http:/ / www. azonano. com/ news.
asp?newsID=18428)
[15] Headrick, J.M.; Diken, E.G.; Walters, R. S.; Hammer, N. I.; Christie, R.A. ; Cui, J.; Myshakin, E.M.; Duncan, M.A.; Johnson, M.A.; Jordan,
K.D. (2005). "Spectral Signatures of Hydrated Proton Vibrations in Water Clusters". Science 308 (5729): 176569.
Bibcode2005Sci...308.1765H. doi:10.1126/science.1113094. PMID15961665.
[16] R.H. Petrucci, W.S. Harwood, and F.G. Herring (2002). General Chemistry (8th ed.). p.41.
[17] "Apollo 11 Mission" (http:/ / www. lpi. usra. edu/ lunar/ missions/ apollo/ apollo_11/ experiments/ swc/ ). Lunar and Planetary Institute.
2009. . Retrieved 2009-06-12.
[18] "Space Travel and Cancer Linked? Stony Brook Researcher Secures NASA Grant to Study Effects of Space Radiation" (http:/ / www. bnl.
gov/ bnlweb/ pubaf/ pr/ PR_display. asp?prID=07-X17). Brookhaven National Laboratory. 12 December 2007. . Retrieved 2009-06-12.
[19] B. Shukitt-Hale, A. Szprengiel, J. Pluhar, B.M. Rabin, and J.A. Joseph. "The effects of proton exposure on neurochemistry and behavior"
(http:/ / biblioteca. universia. net/ ficha. do?id=43176300). Elsevier/COSPAR. . Retrieved 2009-06-12.
[20] N.W. Green and A.R. Frederickson. "A Study of Spacecraft Charging due to Exposure to Interplanetary Protons" (http:/ / trs-new. jpl. nasa.
gov/ dspace/ bitstream/ 2014/ 39501/ 1/ 05-0657. pdf). Jet Propulsion Laboratory. . Retrieved 2009-06-12.
[21] H. Planel (2004). Space and life: an introduction to space biology and medicine (http:/ / books. google. com/ ?id=rnUFZ24RUdYC&
pg=PA132& lpg=PA132& dq=space+ colonization+ proton+ exposure& q=). CRC Press. pp.135138. ISBN0415317592. .
[22] G. Gabrielse (2006). "Antiproton mass measurements". International Journal of Mass Spectrometry 251 (23): 273280.
Bibcode2006IJMSp.251..273G. doi:10.1016/j.ijms.2006.02.013.
97
Proton
98
External links
Particle Data Group (http://pdg.lbl.gov)
Large Hadron Collider (http://www.cern.ch/lhc/)
Neutron
Neutron
The quark structure of the neutron. (The color assignment of individual quarks is not important, only that all three colors are present.)
Classification
Baryon
Composition
Statistics
Fermionic
Interactions
Symbol
n, n0, N0
Antiparticle
Antineutron
Theorized
Ernest Rutherford
Discovered
James Chadwick
Mass
1.674927351(74)1027kg
[3]
939.565378(21)MeV/c2
[3]
1.00866491600(43)u
Mean lifetime
881.5(15)s (free)
Electric charge
0e
0C
<2.91026ecm
Electric polarizability
1.16(15)103fm3
Magnetic moment
0.96623647(23)1026JT1
[3]
1.04187563(25)103B
[3]
1.91304272(45)N
Magnetic polarizability
3.7(20)104fm3
Spin
Isospin
Parity
+1
[1] [2]
[1]
(1920)
(1932)
[3]
[3]
2
2
Neutron
99
Condensed
I(JP)=12(12+)
The neutron is a subatomic hadron particle which has the symbol n or n0, no net electric charge and a mass slightly
larger than that of a proton. With the exception of hydrogen, nuclei of atoms consist of protons and neutrons, which
are therefore collectively referred to as nucleons. The number of protons in a nucleus is the atomic number and
defines the type of element the atom forms. Neutrons are necessary within an atomic nucleus as they bind with
protons via the strong force; protons are unable to bind with each other due to their mutual electromagnetic repulsion
being stronger than the attraction of the strong force. The number of neutrons is the neutron number and determines
the isotope of an element. For example, the abundant carbon-12 isotope has 6 protons and 6 neutrons, while the very
rare radioactive carbon-14 isotope has 6 protons and 8 neutrons.
While bound neutrons in stable nuclei are stable, free neutrons are unstable; they undergo beta decay with a mean
lifetime of just under 15 minutes (881.51.5s).[4] Free neutrons are produced in nuclear fission and fusion.
Dedicated neutron sources like research reactors and spallation sources produce free neutrons for use in irradiation
and in neutron scattering experiments. Even though it is not a chemical element, the free neutron is sometimes
included in tables of nuclides.[5] It is then considered to have an atomic number of zero and a mass number of one,
and is sometimes referred to as neutronium.
The neutron has been the key to nuclear power production. After the neutron was discovered in 1932, it was realized
in 1933 that it might mediate a nuclear chain reaction. In the 1930s, neutrons were used to produce many different
types of nuclear transmutations. When nuclear fission was discovered in 1938, it was soon realized that this might be
the mechanism to produce the neutrons for the chain reaction, if the process also produced neutrons, and this was
proven in 1939, making the path to nuclear power production evident. These events and findings led directly to the
first man-made nuclear chain reaction which was self-sustaining (Chicago Pile-1, 1942) and to the first nuclear
weapons (1945).
Discovery
In 1920, Ernest Rutherford conceptualized the possible existence of the neutron.[2] In particular, Rutherford
considered that the disparity found between the atomic number of an atom and its atomic mass could be explained by
the existence of a neutrally charged particle within the atomic nucleus. He considered the neutron to be a neutral
double consisting in an electron orbiting a proton.
In 1930 Viktor Ambartsumian and Dmitri Ivanenko in USSR found that, contrary to the prevailing opinion of the
time, the nucleus cannot consist of protons and electrons. They proved that some neutral particles must be present
besides the protons.[6]
In 1931, Walther Bothe and Herbert Becker in Germany found that if the very energetic alpha particles emitted from
polonium fell on certain light elements, specifically beryllium, boron, or lithium, an unusually penetrating radiation
was produced. At first this radiation was thought to be gamma radiation, although it was more penetrating than any
gamma rays known, and the details of experimental results were very difficult to interpret on this basis. The next
important contribution was reported in 1932 by Irne Joliot-Curie and Frdric Joliot in Paris. They showed that if
this unknown radiation fell on paraffin, or any other hydrogen-containing compound, it ejected protons of very high
energy. This was not in itself inconsistent with the assumed gamma ray nature of the new radiation, but detailed
quantitative analysis of the data became increasingly difficult to reconcile with such a hypothesis.
In 1932, James Chadwick performed a series of experiments at the University of Cambridge, showing that the
gamma ray hypothesis was untenable. He suggested that the new radiation consisted of uncharged particles of
approximately the mass of the proton, and he performed a series of experiments verifying his suggestion.[7] These
uncharged particles were called neutrons, apparently from the Latin root for neutral and the Greek ending -on (by
imitation of electron and proton).
Neutron
100
The discovery of the neutron explained a puzzle involving the spin of the nitrogen-14 nucleus, which had been
experimentally measured to be 1. It was known that atomic nuclei usually had about half as many positive charges
as if they were composed completely of protons, and in existing models this was often explained by proposing that
nuclei also contained some "nuclear electrons" to neutralize the excess charge. Thus, nitrogen-14 would be
composed of 14 protons and 7 electrons to give it a charge of +7 but a mass of 14 atomic mass units. However, it
was also known that both protons and electrons carried an intrinsic spin of 12, and there was no way to arrange an
odd number (21) of spins 12 to give a spin of 1. Instead, when nitrogen-14 was proposed to consist of 3 pairs of
protons and neutrons, with an additional unpaired neutron and proton each contributing a spin of 12 in the same
direction for a total spin of 1, the model became viable. Soon, nuclear neutrons were used to naturally explain spin
differences in many different nuclides in the same way, and the neutron as a basic structural unit of atomic nuclei
was accepted.
Intrinsic properties
Stability and beta decay
Under the Standard Model of particle physics, because the neutron
consists of three quarks, the only possible decay mode without a
change of baryon number is for one of the quarks to change
flavour via the weak interaction. The neutron consists of two down
quarks with charge 13e and one up quark with charge +23e, and
the decay of one of the down quarks into a lighter up quark can be
achieved by the emission of a W boson. By this means the neutron
decays into a proton (which contains one down and two up
quarks), an electron, and an electron antineutrino.
Outside the nucleus, free neutrons are unstable and have a mean
lifetime of 881.51.5s (about 14 minutes, 42 seconds); therefore
the half-life for this process (which differs from the mean lifetime
by a factor of ln(2) = 0.693) is 611.01.0s (about 10 minutes, 11
seconds).[4] Free neutrons decay by emission of an electron and an
electron antineutrino to become a proton, a process known as beta
decay:[8]
n0 p+ + e + e
Neutrons in unstable nuclei can also decay in this manner. However, inside a nucleus, protons can also transform
into a neutron via inverse beta decay. This transformation occurs by emission of a antielectron (also called positron)
and a neutrino:
p+ n0 + e+ + e
The transformation of a proton to a neutron inside of a nucleus is also possible through electron capture:
p+ + e n0 + e
Positron capture by neutrons in nuclei that contain an excess of neutrons is also possible, but is hindered because
positrons are repelled by the nucleus, and quickly annihilate when they encounter electrons.
When bound inside of a nucleus, the instability of a single neutron to beta decay is balanced against the instability
that would be acquired by the nucleus as a whole if an additional proton were to participate in repulsive interactions
with the other protons that are already present in the nucleus. As such, although free neutrons are unstable, bound
neutrons are not necessarily so. The same reasoning explains why protons, which are stable in empty space, may
transform into neutrons when bound inside of a nucleus.
Neutron
Magnetic moment
Even though the neutron is a neutral particle, the magnetic moment of a neutron is not zero because it is a composite
particle containing three charged quarks.
Anti-neutron
The antineutron is the antiparticle of the neutron. It was discovered by Bruce Cork in the year 1956, a year after the
antiproton was discovered. CPT-symmetry puts strong constraints on the relative properties of particles and
antiparticles, so studying antineutrons yields provide stringent tests on CPT-symmetry. The fractional difference in
the masses of the neutron and antineutron is 96105. Since the difference is only about two standard deviations
away from zero, this does not give any convincing evidence of CPT-violation.[4]
Neutron compounds
Dineutrons and tetraneutrons
The existence of stable clusters of 4 neutrons, or tetraneutrons, has been hypothesised by a team led by
Francisco-Miguel Marqus at the CNRS Laboratory for Nuclear Physics based on observations of the disintegration
of beryllium-14 nuclei. This is particularly interesting because current theory suggests that these clusters should not
be stable.
The dineutron is another hypothetical particle.
101
Neutron
Detection
The common means of detecting a charged particle by looking for a track of ionization (such as in a cloud chamber)
does not work for neutrons directly. Neutrons that elastically scatter off atoms can create an ionization track that is
detectable, but the experiments are not as simple to carry out; other means for detecting neutrons, consisting of
allowing them to interact with atomic nuclei, are more commonly used. The commonly used methods to detect
neutrons can therefore be categorized according to the nuclear processes relied upon, mainly neutron capture or
elastic scattering. A good discussion on neutron detection is found in chapter 14 of the book Radiation Detection and
Measurement by Glenn F. Knoll (John Wiley & Sons, 1979).
Uses
The neutron plays an important role in many nuclear reactions. For example, neutron capture often results in neutron
activation, inducing radioactivity. In particular, knowledge of neutrons and their behavior has been important in the
development of nuclear reactors and nuclear weapons. The fissioning of elements like uranium-235 and
plutonium-239 is caused by their absorption of neutrons.
Cold, thermal and hot neutron radiation is commonly employed in neutron scattering facilities, where the radiation is
used in a similar way one uses X-rays for the analysis of condensed matter. Neutrons are complementary to the latter
in terms of atomic contrasts by different scattering cross sections; sensitivity to magnetism; energy range for
inelastic neutron spectroscopy; and deep penetration into matter.
The development of "neutron lenses" based on total internal reflection within hollow glass capillary tubes or by
reflection from dimpled aluminum plates has driven ongoing research into neutron microscopy and neutron/gamma
ray tomography.[16] [17] [18]
102
Neutron
A major use of neutrons is to excite delayed and prompt gamma rays from elements in materials. This forms the
basis of neutron activation analysis (NAA) and prompt gamma neutron activation analysis (PGNAA). NAA is most
often used to analyze small samples of materials in a nuclear reactor whilst PGNAA is most often used to analyze
subterranean rocks around bore holes and industrial bulk materials on conveyor belts.
Another use of neutron emitters is the detection of light nuclei, particularly the hydrogen found in water molecules.
When a fast neutron collides with a light nucleus, it loses a large fraction of its energy. By measuring the rate at
which slow neutrons return to the probe after reflecting off of hydrogen nuclei, a neutron probe may determine the
water content in soil.
Sources
Because free neutrons are unstable, they can be obtained only from nuclear disintegrations, nuclear reactions, and
high-energy reactions (such as in cosmic radiation showers or accelerator collisions). Free neutron beams are
obtained from neutron sources by neutron transport. For access to intense neutron sources, researchers must go to a
specialist neutron facility that operates a research reactor or a spallation source.
The neutron's lack of total electric charge makes it difficult to steer or accelerate them. Charged particles can be
accelerated, decelerated, or deflected by electric or magnetic fields. These methods have little effect on neutrons
beyond a small effect of an inhomogeneous magnetic field because of the neutron's magnetic moment. Neutrons can
be controlled by methods that include moderation, reflection and velocity selection.
Protection
Exposure to free neutrons can be hazardous, since the interaction of neutrons with molecules in the body can cause
disruption to molecules and atoms, and can also cause reactions which give rise to other forms of radiation (such as
protons). The normal precautions of radiation protection apply: avoid exposure, stay as far from the source as
possible, and keep exposure time to a minimum. Some particular thought must be given to how to protect from
neutron exposure, however. For other types of radiation, e.g. alpha particles, beta particles, or gamma rays, material
of a high atomic number and with high density make for good shielding; frequently lead is used. However, this
approach will not work with neutrons, since the absorption of neutrons does not increase straightforwardly with
atomic number, as it does with alpha, beta, and gamma radiation. Instead one needs to look at the particular
interactions neutrons have with matter (see the section on detection above). For example, hydrogen-rich materials are
often used to shield against neutrons, since ordinary hydrogen both scatters and slows neutrons. This often means
that simple concrete blocks or even paraffin-loaded plastic blocks afford better protection from neutrons than do far
more dense materials. After slowing, neutrons may then be absorbed with an isotope which has high affinity for slow
neutrons without causing secondary capture-radiation, such as lithium-6.
Hydrogen-rich ordinary water affects neutron absorption in nuclear fission reactors: usually neutrons are so strongly
absorbed by normal water that fuel-enrichment with fissionable isotope is required. The deuterium in heavy water
has a very much lower absorption affinity for neutrons than does protium (normal light hydrogen). Deuterium is
therefore used in CANDU-type reactors, in order to slow (moderate) neutron velocity, to increase the probability of
nuclear fission compared to neutron capture.
103
Neutron
Production
Various nuclides become more stable by expelling neutrons as a decay
mode; this is known as neutron emission, and happens commonly
during spontaneous fission.
Cosmic radiation interacting with the Earth's atmosphere continuously
generates neutrons that can be detected at the surface. Even stronger
neutron radiation is produced at the surface of Mars where the
atmosphere is thick enough to generate neutrons from cosmic ray
spallation, but not thick enough to provide significant protection from
Institut LaueLangevin (ILL) in Grenoble,
the neutrons produced. These neutrons not only produce a Martian
France one of the most important neutron
surface neutron radiation hazard from direct downward-going neutron
research facilities worldwide
radiation, but also a significant hazard from reflection of neutrons from
the Martian surface, which will produce reflected neutron radiation penetrating upward into a Martian craft or habitat
from the floor.[19]
Nuclear fission reactors naturally produce free neutrons; their role is to sustain the energy-producing chain reaction.
The intense neutron radiation can also be used to produce various radioisotopes through the process of neutron
activation, which is a type of neutron capture.
Experimental nuclear fusion reactors produce free neutrons as a waste product. However, it is these neutrons that
possess most of the energy, and converting that energy to a useful form has proved a difficult engineering challenge.
Fusion reactors which generate neutrons are likely to create around twice the amount of radioactive waste of a
fission reactor, but the waste is composed of neutron-activated lighter isotopes, which have relatively short (50100
years) decay periods as compared to typical half lives of 10,000 years for fission waste, which is long primarily due
to the long half life of alpha-emitting transuranic actinides.[20]
Neutron temperature
Thermal neutrons
A thermal neutron is a free neutron that is Boltzmann distributed with kT = 0.0253eV (4.01021J) at room
temperature. This gives characteristic (not average, or median) speed of 2.2km/s. The name 'thermal' comes from
their energy being that of the room temperature gas or material they are permeating. (see kinetic theory for energies
and speeds of molecules). After a number of collisions (often in the range of 1020) with nuclei, neutrons arrive at
this energy level, provided that they are not absorbed.
In many substances, thermal neutrons have a much larger effective cross-section than faster neutrons, and can
therefore be absorbed more easily by any atomic nuclei that they collide with, creating a heavier and often
unstable isotope of the chemical element as a result.
Most fission reactors use a neutron moderator to slow down, or thermalize the neutrons that are emitted by nuclear
fission so that they are more easily captured, causing further fission. Others, called fast breeder reactors, use fission
energy neutrons directly.
104
Neutron
Cold neutrons
Cold neutrons are thermal neutrons that have been equilibrated in a very cold substance such as liquid deuterium.
Such a cold source is placed in the moderator of a research reactor or spallation source. Cold neutrons are
particularly valuable for neutron scattering experiments.
Ultracold neutrons
Ultracold neutrons are produced by inelastically scattering cold neutrons in substances with a temperature of a few
kelvins, such as solid deuterium or superfluid helium. An alternative production method is the mechanical
deceleration of cold neutrons.
Fusion neutrons
D-T (deuterium-tritium) fusion is the fusion
reaction that produces the most energetic
neutrons, with 14.1 MeV of kinetic energy
and traveling at 17% of the speed of light.
D-T fusion is also the easiest fusion reaction
to ignite, reaching near-peak rates even
when the deuterium and tritium nuclei have
only a thousandth as much kinetic energy as
the 14.1 MeV that will be produced.
14.1 MeV neutrons have about 10 times as
much energy as fission neutrons, and are
very effective at fissioning even non-fissile
heavy nuclei, and these high-energy fissions
produce more neutrons on average than
The fusion reaction rate increases rapidly with temperature until it maximizes and
fissions by lower-energy neutrons. This
then gradually drops off. The DT rate peaks at a lower temperature (about 70keV,
makes D-T fusion neutron sources such as
or 800 million kelvins) and at a higher value than other reactions commonly
proposed tokamak power reactors useful for
considered for fusion energy.
transmutation of transuranic waste. 14.1
MeV neutrons can also produce neutrons by knocking them loose from nuclei.
On the other hand, these very high energy neutrons are less likely to simply be captured without causing fission or
spallation. For these reasons, nuclear weapon design extensively utilizes D-T fusion 14.1 MeV neutrons to cause
more fission. Fusion neutrons are able to cause fission in ordinarily non-fissile materials, such as depleted uranium
(uranium-238), and these materials have been used in the jackets of thermonuclear weapons. Fusion neutrons also
can cause fission in substances that are unsuitable or difficult to make into primary fission bombs, such as reactor
grade plutonium. This physical fact thus causes ordinary non-weapons grade materials to become of concern in
certain nuclear proliferation discussions and treaties.
105
Neutron
106
Other fusion reactions produce much less energetic neutrons. D-D fusion produces a 2.45 MeV neutron and helium-3
half of the time, and produces tritium and a proton but no neutron the other half of the time. D-3He fusion produces
no neutron.
Intermediate-energy neutrons
A fission energy neutron that has slowed
down but not yet reached thermal energies is
called an epithermal neutron.
Cross sections for both capture and fission
reactions often have multiple resonance
peaks at specific energies in the epithermal
energy range. These are of less significance
in a fast neutron reactor where most
neutrons are absorbed before slowing down
to this range, or in a well-moderated thermal
reactor where epithermal neutrons mostly
interact with moderator nuclei, not with
either fissile or fertile actinide nuclides.
However, in a partially moderated reactor
with more interactions of epithermal
neutrons with heavy metal nuclei, there are
greater possibilities for transient changes in
reactivity which might make reactor control
more difficult.
High-energy neutrons
These neutrons have more energy than fission energy neutrons and are generated as secondary particles by particle
accelerators or in the atmosphere from cosmic rays. They can have energies as high as tens of joules per neutron.
These neutrons are extremely efficient at ionization and far more likely to cause cell death than X-rays or protons.[21]
[22]
References
[1] 1935 Nobel Prize in Physics (http:/ / nobelprize. org/ nobel_prizes/ physics/ laureates/ 1935/ )
[2] http:/ / chemed. chem. purdue. edu/ genchem/ history/ rutherford. html
[3] P.J. Mohr, B.N. Taylor, and D.B. Newell (2011), "The 2010 CODATA Recommended Values of the Fundamental Physical Constants" (Web
Version 6.0). This database was developed by J. Baker, M. Douma, and S. Kotochigova. Available: http:/ / physics. nist. gov/ constants
[Thursday, 02-Jun-2011 21:00:12 EDT]. National Institute of Standards and Technology, Gaithersburg, MD 20899.
[4] K. Nakamura et al. (Particle Data Group) (http:/ / pdg. lbl. gov/ 2011/ listings/ rpp2011-list-n. pdf), JP G 37, 075021 (2010) and 2011 partial
update for the 2012 edition
[5] Nudat 2 (http:/ / www. nndc. bnl. gov/ nudat2). Nndc.bnl.gov. Retrieved on 2010-12-04.
Neutron
[6] "V. A. Ambartsumian a life in science" (http:/ / www. springerlink. com/ content/ ek2q156624661848/ fulltext. pdf). Astrophysics 51: 280.
2008. Bibcode2008Ap.....51..280T. doi:10.1007/s10511-008-9016-6. .
[7] Chadwick, James (1932). "Possible Existence of a Neutron". Nature 129 (3252): 312. Bibcode1932Natur.129Q.312C.
doi:10.1038/129312a0.
[8] Particle Data Group Summary Data Table on Baryons (http:/ / pdg. lbl. gov/ 2007/ tables/ bxxx. pdf)
[9] "Pear-shaped particles probe big-bang mystery" (http:/ / www. sussex. ac. uk/ press_office/ media/ media537. shtml) (Press release).
University of Sussex. 20 February 2006. . Retrieved 2009-12-14.
[10] A cryogenic experiment to search for the EDM of the neutron (http:/ / hepwww. rl. ac. uk/ EDM/ index_files/ CryoEDM. htm)
[11] Search for the neutron electric dipole moment: nEDM (http:/ / nedm. web. psi. ch/ )
[12] SNS Neutron EDM Experiment (http:/ / p25ext. lanl. gov/ edm/ edm. html)
[13] Measurement of the Neutron Electric Dipole Moment (http:/ / nrd. pnpi. spb. ru/ LabSereb/ neutronedm. htm)
[14] G.A. Miller (2007). "Charge Densities of the Neutron and Proton". Physical Review Letters 99: 112001. Bibcode2007PhRvL..99k2001M.
doi:10.1103/PhysRevLett.99.112001.
[15] Felipe J. Llanes-Estrada, Gaspar Moreno Navarro. (2011). "Cubic neutrons". arXiv:1108.1859v1[nucl-th].
[16] Kumakhov, M. A.; Sharov, V. A. (1992). "A neutron lens". Nature 357 (6377): 390391. Bibcode1992Natur.357..390K.
doi:10.1038/357390a0.
[17] Physorg.com, "New Way of 'Seeing': A 'Neutron Microscope'" (http:/ / www. physorg. com/ news599. html)
[18] NASA.gov: "NASA Develops a Nugget to Search for Life in Space" (http:/ / www. nasa. gov/ vision/ earth/ technologies/ nuggets. html)
[19] Clowdsley, MS; Wilson, JW; Kim, MH; Singleterry, RC; Tripathi, RK; Heinbockel, JH; Badavi, FF; Shinn, JL (2001). "Neutron
Environments on the Martian Surface" (http:/ / www. physicamedica. com/ VOLXVII_S1/ 20-CLOWDSLEY et alii. pdf). Physica Medica 17
(Suppl 1): 946. PMID11770546. .
[20] Science/Nature | Q&A: Nuclear fusion reactor (http:/ / news. bbc. co. uk/ 1/ hi/ sci/ tech/ 4627237. stm). BBC News (2006-02-06). Retrieved
on 2010-12-04.
[21] "Facing up to secondary neutrons" (http:/ / medicalphysicsweb. org/ cws/ article/ research/ 34364). Medical Physics Web. May 23, 2008. .
Retrieved 2011-02-08.
[22] "Expand+Overview of secondary neutron production relevant to shielding in space" (http:/ / rpd. oxfordjournals. org/ content/ 116/ 1-4/ 140.
full). Radiation Protection Dosimetry 116 (1-4): 140143. 20 December 2005. doi:10.1093/rpd/nci033. . Retrieved 2011-02-08.
Further reading
Annotated bibliography for neutrons from the Alsos Digital Library for Nuclear Issues (http://alsos.wlu.edu/
qsearch.aspx?browse=science/Neutrons)
Knoll, G. F. (2000) Radiation Detection and Measurement
Krane, K. S. (1998) Introductory Nuclear Physics
Squires, G. L. (1997) Introduction to the Theory of Thermal Neutron Scattering
Dewey, M. S., Gilliam, D. M., Nico, J. S., Snow, M. S., Wietfeldt, F. E. NIST Neutron Lifetime Experiment
107
Electron
108
Electron
Electron
Experiments with a Crookes tube first demonstrated the particle nature of electrons. In this illustration, the profile of the cross-shaped target is
[1]
projected against the tube face at right by a beam of electrons.
[2]
Composition
Elementary particle
Statistics
Fermionic
Generation
First
Interactions
Symbol
e,
Antiparticle
Theorized
[3]
Richard Laming (18381851),
[4] [5]
G. Johnstone Stoney (1874) and others.
Discovered
J. J. Thomson (1897)
Mass
[7]
9.10938291(40)1031kg
4 [7]
5.4857990946(22)10 u
[8]
[1822.8884845(14)]1u
[7]
0.510998928(11)MeV/c2
Electric charge
[9]
1
[7]
1.602176565(35)1019C
10
4.80320451(10)10 esu
Magnetic moment
[7]
1.00115965218076(27) B
Spin
[6]
The electron (symbol: e) is a subatomic particle with a negative elementary electric charge. It has no known
components or substructure; in other words, it is generally thought to be an elementary particle.[2] An electron has a
mass that is approximately 1/1836 that of the proton.[10] The intrinsic angular momentum (spin) of the electron is a
half-integer value in units of , which means that it is a fermion. The antiparticle of the electron is called the
positron; it is identical to the electron except that it carries electrical and other charges of the opposite sign. When an
electron collides with a positron, both particles may either scatter off each other or be totally annihilated, producing a
pair (or more) of gamma ray photons. Electrons, which belong to the first generation of the lepton particle family,[11]
Electron
participate in gravitational, electromagnetic and weak interactions.[12] Electrons, like all matter, have quantum
mechanical properties of both particles and waves, so they can collide with other particles and can be diffracted like
light. However, this duality is best demonstrated in experiments with electrons, due to their tiny mass. Since an
electron is a fermion, no two electrons can occupy the same quantum state, in accordance with the Pauli exclusion
principle.[11]
The concept of an indivisible quantity of electric charge was theorized to explain the chemical properties of atoms,
beginning in 1838 by British natural philosopher Richard Laming;[4] the name electron was introduced for this
charge in 1894 by Irish physicist George Johnstone Stoney. The electron was identified as a particle in 1897 by J. J.
Thomson and his team of British physicists.[6] [13] [14]
In many physical phenomena, such as electricity, magnetism, and thermal conductivity, electrons play an essential
role. An electron in motion relative to an observer generates a magnetic field, and will be deflected by external
magnetic fields. When an electron is accelerated, it can absorb or radiate energy in the form of photons. Electrons,
together with atomic nuclei made of protons and neutrons, make up atoms. However, electrons contribute less than
0.06% to an atom's total mass. The attractive Coulomb force between an electron and a proton causes electrons to be
bound into atoms. The exchange or sharing of the electrons between two or more atoms is the main cause of
chemical bonding.[15]
According to theory, most electrons in the universe were created in the big bang, but they may also be created
through beta decay of radioactive isotopes and in high-energy collisions, for instance when cosmic rays enter the
atmosphere. Electrons may be destroyed through annihilation with positrons, and may be absorbed during
nucleosynthesis in stars. Laboratory instruments are capable of containing and observing individual electrons as well
as electron plasma, whereas dedicated telescopes can detect electron plasma in outer space. Electrons have many
applications, including welding, cathode ray tubes, electron microscopes, radiation therapy, lasers and particle
accelerators.
History
The ancient Greeks noticed that amber attracted small objects when rubbed with fur. Apart from lightning, this
phenomenon is humanity's earliest recorded experience with electricity.[16] In his 1600 treatise De Magnete, the
English scientist William Gilbert coined the New Latin term electricus, to refer to this property of attracting small
objects after being rubbed.[17] Both electric and electricity are derived from the Latin lectrum (also the root of the
alloy of the same name), which came from the Greek word (lektron) for amber.
In 1737, C. F. du Fay and Hawksbee independently discovered what they believed to be two kinds of frictional
electricity; one generated from rubbing glass, the other from rubbing resin. From this, Du Fay theorized that
electricity consists of two electrical fluids, "vitreous" and "resinous", that are separated by friction and that neutralize
each other when combined.[18] A decade later Benjamin Franklin proposed that electricity was not from different
types of electrical fluid, but the same electrical fluid under different pressures. He gave them the modern charge
nomenclature of positive and negative respectively.[19] Franklin thought that the charge carrier was positive.[20]
Between 1838 and 1851, British natural philosopher Richard Laming developed the idea that an atom is composed of
a core of matter surrounded by subatomic particles that had unit electric charges.[3] Beginning in 1846, German
physicist William Weber theorized that electricity was composed of positively and negatively charged fluids, and
their interaction was governed by the inverse square law. After studying the phenomenon of electrolysis in 1874,
Irish physicist George Johnstone Stoney suggested that there existed a "single definite quantity of electricity", the
charge of a monovalent ion. He was able to estimate the value of this elementary charge e by means of Faraday's
laws of electrolysis.[21] However, Stoney believed these charges were permanently attached to atoms and could not
be removed. In 1881, German physicist Hermann von Helmholtz argued that both positive and negative charges
were divided into elementary parts, each of which "behaves like atoms of electricity".[4]
109
Electron
In 1894, Stoney coined the term electron to describe these elementary charges, saying, "... an estimate was made of
the actual amount of this most remarkable fundamental unit of electricity, for which I have since ventured to suggest
the name electron".[22] The word electron is a combination of the word electric and the suffix -on, with the latter
now used to designate a subatomic particle, such as a proton or neutron.[23] [24]
Discovery
The German physicist Johann Wilhelm Hittorf undertook the study of
electrical conductivity in rarefied gases. In 1869, he discovered a glow
emitted from the cathode that increased in size with decrease in gas
pressure. In 1876, the German physicist Eugen Goldstein showed that
the rays from this glow cast a shadow, and he dubbed the rays cathode
rays.[26] During the 1870s, the English chemist and physicist Sir
William Crookes developed the first cathode ray tube to have a high
vacuum inside.[27] He then showed that the luminescence rays
A beam of electrons deflected in a circle by a
[25]
appearing within the tube carried energy and moved from the cathode
magnetic field
to the anode. Furthermore, by applying a magnetic field, he was able to
deflect the rays, thereby demonstrating that the beam behaved as though it were negatively charged.[28] [29] In 1879,
he proposed that these properties could be explained by what he termed 'radiant matter'. He suggested that this was a
fourth state of matter, consisting of negatively charged molecules that were being projected with high velocity from
the cathode.[30]
The German-born British physicist Arthur Schuster expanded upon Crookes' experiments by placing metal plates
parallel to the cathode rays and applying an electric potential between the plates. The field deflected the rays toward
the positively charged plate, providing further evidence that the rays carried negative charge. By measuring the
amount of deflection for a given level of current, in 1890 Schuster was able to estimate the charge-to-mass ratio of
the ray components. However, this produced a value that was more than a thousand times greater than what was
expected, so little credence was given to his calculations at the time.[28] [31]
In 1896, the British physicist J. J. Thomson, with his colleagues John S. Townsend and H. A. Wilson,[13] performed
experiments indicating that cathode rays really were unique particles, rather than waves, atoms or molecules as was
believed earlier.[6] Thomson made good estimates of both the charge e and the mass m, finding that cathode ray
particles, which he called "corpuscles," had perhaps one thousandth of the mass of the least massive ion known:
hydrogen.[6] [14] He showed that their charge to mass ratio, e/m, was independent of cathode material. He further
showed that the negatively charged particles produced by radioactive materials, by heated materials and by
illuminated materials were universal.[6] [32] The name electron was again proposed for these particles by the Irish
physicist George F. Fitzgerald, and the name has since gained universal acceptance.[28]
While studying naturally fluorescing minerals in 1896, the French physicist Henri Becquerel discovered that they
emitted radiation without any exposure to an external energy source. These radioactive materials became the subject
of much interest by scientists, including the New Zealand physicist Ernest Rutherford who discovered they emitted
particles. He designated these particles alpha and beta, on the basis of their ability to penetrate matter.[33] In 1900,
Becquerel showed that the beta rays emitted by radium could be deflected by an electric field, and that their
mass-to-charge ratio was the same as for cathode rays.[34] This evidence strengthened the view that electrons existed
as components of atoms.[35] [36]
The electron's charge was more carefully measured by the American physicist Robert Millikan and Harvey Fletcher
in their oil-drop experiment of 1909, the results of which were published in 1911. This experiment used an electric
field to prevent a charged droplet of oil from falling as a result of gravity. This device could measure the electric
charge from as few as 1150 ions with an error margin of less than 0.3%. Comparable experiments had been done
earlier by Thomson's team,[6] using clouds of charged water droplets generated by electrolysis,[13] and in 1911 by
110
Electron
111
Abram Ioffe, who independently obtained the same result as Millikan using charged microparticles of metals, then
published his results in 1913.[37] However, oil drops were more stable than water drops because of their slower
evaporation rate, and thus more suited to precise experimentation over longer periods of time.[38]
Around the beginning of the twentieth century, it was found that under certain conditions a fast moving charged
particle caused a condensation of supersaturated water vapor along its path. In 1911, Charles Wilson used this
principle to devise his cloud chamber, allowing the tracks of charged particles, such as fast-moving electrons, to be
photographed.[39]
Atomic theory
By 1914, experiments by physicists Ernest Rutherford, Henry Moseley,
James Franck and Gustav Hertz had largely established the structure of
an atom as a dense nucleus of positive charge surrounded by
lower-mass electrons.[40] In 1913, Danish physicist Niels Bohr
postulated that electrons resided in quantized energy states, with the
energy determined by the angular momentum of the electron's orbits
about the nucleus. The electrons could move between these states, or
orbits, by the emission or absorption of photons at specific frequencies.
By means of these quantized orbits, he accurately explained the
spectral lines of the hydrogen atom.[41] However, Bohr's model failed
to account for the relative intensities of the spectral lines and it was
unsuccessful in explaining the spectra of more complex atoms.[40]
Electron
Quantum mechanics
In his 1924 dissertation Recherches sur la thorie des quanta (Research on Quantum Theory), French physicist
Louis de Broglie hypothesized that all matter possesses a De Broglie wave similar to light.[49] That is, under the
appropriate conditions, electrons and other matter would show properties of either particles or waves. The
corpuscular properties of a particle are demonstrated when it is shown to have a localized position in space along its
trajectory at any given moment.[50] Wave-like nature is observed, for example, when a beam of light is passed
through parallel slits and creates interference patterns. In 1927, the interference effect was demonstrated with a beam
of electrons by English physicist George Paget Thomson with a thin metal film and by American physicists Clinton
Davisson and Lester Germer using a crystal of nickel.[51]
The success of de Broglie's prediction led to the publication, by Erwin
Schrdinger in 1926, of the Schrdinger equation that successfully
describes how electron waves propagated.[52] Rather than yielding a
solution that determines the location of an electron over time, this
wave equation can be used to predict the probability of finding an
electron near a position. This approach was later called quantum
mechanics, which provided an extremely close derivation to the energy
states of an electron in a hydrogen atom.[53] Once spin and the
interaction between multiple electrons were considered, quantum
mechanics allowed the configuration of electrons in atoms with higher
atomic numbers than hydrogen to be successfully predicted.[54]
In 1928, building on Wolfgang Pauli's work, Paul Dirac produced a
model of the electron - the Dirac equation, consistent with relativity
theory, by applying relativistic and symmetry considerations to the
In quantum mechanics, the behavior of an
hamiltonian formulation of the quantum mechanics of the
electron in an atom is described by an orbital,
which is a probability distribution rather than an
electro-magnetic field.[55] In order to resolve some problems within his
orbit. In the figure, the shading indicates the
relativistic equation, in 1930 Dirac developed a model of the vacuum
relative probability to "find" the electron, having
as an infinite sea of particles having negative energy, which was
the energy corresponding to the given quantum
dubbed the Dirac sea. This led him to predict the existence of a
numbers, at that point.
positron, the antimatter counterpart of the electron.[56] This particle
was discovered in 1932 by Carl D. Anderson, who proposed calling standard electrons negatrons, and using electron
as a generic term to describe both the positively and negatively charged variants. This usage of the term 'negatron' is
still occasionally encountered today, and it may be shortened to 'negaton'.[57] [58]
In 1947 Willis Lamb, working in collaboration with graduate student Robert Rutherford, found that certain quantum
states of hydrogen atom, which should have the same energy, were shifted in relation to each other, the difference
being the Lamb shift. About the same time, Polykarp Kusch, working with Henry M. Foley, discovered the magnetic
moment of the electron is slightly larger than predicted by Dirac's theory. This small difference was later called
anomalous magnetic dipole moment of the electron. To resolve these issues, a refined theory called quantum
electrodynamics was developed by Sin-Itiro Tomonaga, Julian Schwinger and Richard P. Feynman in the late
1940s.[59]
112
Electron
113
Particle accelerators
With the development of the particle accelerator during the first half of the twentieth century, physicists began to
delve deeper into the properties of subatomic particles.[60] The first successful attempt to accelerate electrons using
electromagnetic induction was made in 1942 by Donald Kerst. His initial betatron reached energies of 2.3MeV,
while subsequent betatrons achieved 300MeV. In 1947, synchrotron radiation was discovered with a 70MeV
electron synchrotron at General Electric. This radiation was caused by the acceleration of electrons, moving near the
speed of light, through a magnetic field.[61]
With a beam energy of 1.5GeV, the first high-energy particle collider was ADONE, which began operations in
1968.[62] This device accelerated electrons and positrons in opposite directions, effectively doubling the energy of
their collision when compared to striking a static target with an electron.[63] The Large Electron-Positron Collider
(LEP) at CERN, which was operational from 1989 to 2000, achieved collision energies of 209GeV and made
important measurements for the Standard Model of particle physics.[64] [65]
Characteristics
Classification
In the Standard Model of particle physics,
electrons belong to the group of subatomic
particles called leptons, which are believed
to be fundamental or elementary particles.
Electrons have the lowest mass of any
charged lepton (or electrically charged
particle of any type) and belong to the
first-generation of fundamental particles.[66]
The second and third generation contain
charged leptons, the muon and the tau,
which are identical to the electron in charge,
spin and interactions, but are more massive.
Leptons differ from the other basic
constituent of matter, the quarks, by their
lack of strong interaction. All members of
the lepton group are fermions, because they
all have half-odd integer spin; the electron
has spin 12.[67]
Fundamental properties
Electron
114
has the same properties as the electron but with a positive rather than negative charge.[67] [68]
The electron has an intrinsic angular momentum or spin of 12.[68] This property is usually stated by referring to the
electron as a spin-12 particle.[67] For such particles the spin magnitude is 32.[72] while the result of the
measurement of a projection of the spin on any axis can only be 2. In addition to spin, the electron has an intrinsic
magnetic moment along its spin axis.[68] It is approximately equal to one Bohr magneton,[73] [74] which is a physical
constant equal to 9.27400915(23)1024joules per tesla.[68] The orientation of the spin with respect to the
momentum of the electron defines the property of elementary particles known as helicity.[75]
The electron has no known substructure.[2] [76] Hence, it is defined or assumed to be a point particle with a point
charge and no spatial extent.[11] Observation of a single electron in a Penning trap shows the upper limit of the
particle's radius is 1022 meters.[77] There is a physical constant called the "classical electron radius", with the much
larger value of 2.81791015m. However, the terminology comes from a simplistic calculation that ignores the
effects of quantum mechanics; in reality, the so-called classical electron radius has little to do with the true
fundamental structure of the electron.[78] [79]
There are elementary particles that spontaneously decay into less massive particles. An example is the muon, which
decays into an electron, a neutrino and an antineutrino, with a mean lifetime of 2.2106 seconds. However, the
electron is thought to be stable on theoretical grounds: the electron is the least massive particle with non-zero electric
charge, so its decay would violate charge conservation.[80] The experimental lower bound for the electron's mean
lifetime is 4.61026 years, at a 90% confidence level.[81]
Quantum properties
As with all particles, electrons can act as waves. This is called the waveparticle duality and can be demonstrated
using the double-slit experiment. The wave-like nature of the electron allows it to pass through two parallel slits
simultaneously, rather than just one slit as would be the case for a classical particle. In quantum mechanics, the
wave-like property of one particle can be described mathematically as a complex-valued function, the wave function,
commonly denoted by the Greek letter psi (). When the absolute value of this function is squared, it gives the
probability that a particle will be observed near a locationa probability density.[82]
Electrons are identical particles because they cannot be distinguished
from each other by their intrinsic physical properties. In quantum
mechanics, this means that a pair of interacting electrons must be able
to swap positions without an observable change to the state of the
system. The wave function of fermions, including electrons, is
antisymmetric, meaning that it changes sign when two electrons are
swapped; that is, (r1, r2) = (r2, r1), where the variables r1 and r2
correspond to the first and second electrons, respectively. Since the
absolute value is not changed by a sign swap, this corresponds to equal
probabilities. Bosons, such as the photon, have symmetric wave
functions instead.[82]
Electron
115
Virtual particles
Physicists believe that empty space may be continually creating pairs of virtual particles, such as a positron and
electron, which rapidly annihilate each other shortly thereafter.[83] The combination of the energy variation needed to
create these particles, and the time during which they exist, fall under the threshold of detectability expressed by the
Heisenberg uncertainty relation, Et. In effect, the energy needed to create these virtual particles, E, can be
"borrowed" from the vacuum for a period of time, t, so that their product is no more than the reduced Planck
constant, 6.61016eVs. Thus, for a virtual electron, t is at most 1.31021s.[84]
While an electronpositron virtual pair is in existence, the coulomb
force from the ambient electric field surrounding an electron causes a
created positron to be attracted to the original electron, while a created
electron experiences a repulsion. This causes what is called vacuum
polarization. In effect, the vacuum behaves like a medium having a
dielectric permittivity more than unity. Thus the effective charge of an
electron is actually smaller than its true value, and the charge decreases
with increasing distance from the electron.[85] [86] This polarization
was confirmed experimentally in 1997 using the Japanese TRISTAN
particle accelerator.[87] Virtual particles cause a comparable shielding
effect for the mass of the electron.[88]
The interaction with virtual particles also explains the small (about
0.1%) deviation of the intrinsic magnetic moment of the electron from the Bohr magneton (the anomalous magnetic
moment).[73] [89] The extraordinarily precise agreement of this predicted difference with the experimentally
determined value is viewed as one of the great achievements of quantum electrodynamics.[90]
In classical physics, the angular momentum and magnetic moment of an object depend upon its physical dimensions.
Hence, the concept of a dimensionless electron possessing these properties might seem inconsistent. The apparent
paradox can be explained by the formation of virtual photons in the electric field generated by the electron. These
photons cause the electron to shift about in a jittery fashion (known as zitterbewegung),[91] which results in a net
circular motion with precession. This motion produces both the spin and the magnetic moment of the electron.[11] [92]
In atoms, this creation of virtual photons explains the Lamb shift observed in spectral lines.[85]
Interaction
An electron generates an electric field that exerts an attractive force on a particle with a positive charge, such as the
proton, and a repulsive force on a particle with a negative charge. The strength of this force is determined by
Coulomb's inverse square law.[93] When an electron is in motion, it generates a magnetic field.[94] The
Ampre-Maxwell law relates the magnetic field to the mass motion of electrons (the current) with respect to an
observer. It is this property of induction which supplies the magnetic field that drives an electric motor.[95] The
electromagnetic field of an arbitrary moving charged particle is expressed by the LinardWiechert potentials, which
are valid even when the particle's speed is close to that of light (relativistic).
Electron
116
An inelastic collision between a photon (light) and a solitary (free) electron is called Compton scattering. This
collision results in a transfer of momentum and energy between the particles, which modifies the wavelength of the
photon by an amount called the Compton shift.[102] The maximum magnitude of this wavelength shift is h/mec,
which is known as the Compton wavelength.[103] For an electron, it has a value of 2.431012m.[68] When the
wavelength of the light is long (for instance, the wavelength of the visible light is 0.40.7m) the wavelength shift
becomes negligible. Such interaction between the light and free electrons is called Thomson scattering or Linear
Thomson scattering.[104]
The relative strength of the electromagnetic interaction between two charged particles, such as an electron and a
proton, is given by the fine-structure constant. This value is a dimensionless quantity formed by the ratio of two
energies: the electrostatic energy of attraction (or repulsion) at a separation of one Compton wavelength, and the rest
Electron
energy of the charge. It is given by 7.297353103, which is approximately equal to 1137.[68]
When electrons and positrons collide, they annihilate each other, giving rise to two or more gamma ray photons. If
the electron and positron have negligible momentum, a positronium atom can form before annihilation results in two
or three gamma ray photons totalling 1.022MeV.[105] [106] On the other hand, high-energy photons may transform
into an electron and a positron by a process called pair production, but only in the presence of a nearby charged
particle, such as a nucleus.[107] [108]
In the theory of electroweak interaction, the left-handed component of electron's wavefunction forms a weak isospin
doublet with the electron neutrino. This means that during weak interactions, electron neutrinos behave like
electrons. Either member of this doublet can undergo a charged current interaction by emitting or absorbing a W and
be converted into the other member. Charge is conserved during this reaction because the W boson also carries a
charge, canceling out any net change during the transmutation. Charged current interactions are responsible for the
phenomenon of beta decay in a radioactive atom. Both the electron and electron neutrino can undergo a neutral
current interaction via a Z0 exchange, and this is responsible for neutrino-electron elastic scattering.[109]
117
Electron
allowing the formation of molecules.[15] Within a molecule, electrons move under the influence of several nuclei,
and occupy molecular orbitals; much as they can occupy atomic orbitals in isolated atoms.[115] A fundamental factor
in these molecular structures is the existence of electron pairs. These are electrons with opposed spins, allowing them
to occupy the same molecular orbital without violating the Pauli exclusion principle (much like in atoms). Different
molecular orbitals have different spatial distribution of the electron density. For instance, in bonded pairs (i.e. in the
pairs that actually bind atoms together) electrons can be found with the maximal probability in a relatively small
volume between the nuclei. On the contrary, in non-bonded pairs electrons are distributed in a large volume around
nuclei.[116]
Conductivity
If a body has more or fewer electrons than are required to balance the
positive charge of the nuclei, then that object has a net electric charge.
When there is an excess of electrons, the object is said to be negatively
charged. When there are fewer electrons than the number of protons in
nuclei, the object is said to be positively charged. When the number of
electrons and the number of protons are equal, their charges cancel
each other and the object is said to be electrically neutral. A
macroscopic body can develop an electric charge through rubbing, by
the triboelectric effect.[120]
Independent electrons moving in vacuum are termed free electrons.
Electrons in metals also behave as if they were free. In reality the
particles that are commonly termed electrons in metals and other solids
A lightning discharge consists primarily of a flow
[117]
are quasi-electronsquasi-particles, which have the same electrical
of electrons.
The electric potential needed
charge, spin and magnetic moment as real electrons but may have a
for lightning may be generated by a triboelectric
[118] [119]
effect.
different mass.[121] When free electronsboth in vacuum and
metalsmove, they produce a net flow of charge called an electric
current, which generates a magnetic field. Likewise a current can be created by a changing magnetic field. These
interactions are described mathematically by Maxwell's equations.[122]
At a given temperature, each material has an electrical conductivity that determines the value of electric current
when an electric potential is applied. Examples of good conductors include metals such as copper and gold, whereas
glass and Teflon are poor conductors. In any dielectric material, the electrons remain bound to their respective atoms
and the material behaves as an insulator. Most semiconductors have a variable level of conductivity that lies between
the extremes of conduction and insulation.[123] On the other hand, metals have an electronic band structure
containing partially filled electronic bands. The presence of such bands allows electrons in metals to behave as if
they were free or delocalized electrons. These electrons are not associated with specific atoms, so when an electric
field is applied, they are free to move like a gas (called Fermi gas)[124] through the material much like free electrons.
Because of collisions between electrons and atoms, the drift velocity of electrons in a conductor is on the order of
millimeters per second. However, the speed at which a change of current at one point in the material causes changes
in currents in other parts of the material, the velocity of propagation, is typically about 75% of light speed.[125] This
occurs because electrical signals propagate as a wave, with the velocity dependent on the dielectric constant of the
material.[126]
Metals make relatively good conductors of heat, primarily because the delocalized electrons are free to transport
thermal energy between atoms. However, unlike electrical conductivity, the thermal conductivity of a metal is nearly
independent of temperature. This is expressed mathematically by the Wiedemann-Franz law,[124] which states that
the ratio of thermal conductivity to the electrical conductivity is proportional to the temperature. The thermal
118
Electron
disorder in the metallic lattice increases the electrical resistivity of the material, producing a temperature dependence
for electrical current.[127]
When cooled below a point called the critical temperature, materials can undergo a phase transition in which they
lose all resistivity to electrical current, in a process known as superconductivity. In BCS theory, this behavior is
modeled by pairs of electrons entering a quantum state known as a BoseEinstein condensate. These Cooper pairs
have their motion coupled to nearby matter via lattice vibrations called phonons, thereby avoiding the collisions with
atoms that normally create electrical resistance.[128] (Cooper pairs have a radius of roughly 100nm, so they can
overlap each other.)[129] However, the mechanism by which higher temperature superconductors operate remains
uncertain.
Electrons inside conducting solids, which are quasi-particles themselves, when tightly confined at temperatures close
to absolute zero, behave as though they had split into two other quasiparticles: spinons and holons.[130] [131] The
former carries spin and magnetic moment, while the latter electrical charge.
The effects of special relativity are based on a quantity known as the Lorentz factor, defined as
where v is the speed of the particle. The kinetic energy Ke of an electron moving with velocity v is:
where me is the mass of electron. For example, the Stanford linear accelerator can accelerate an electron to roughly
51GeV.[133] Since an electron behaves as a wave, at a given velocity it has a characteristic de Broglie wavelength.
This is given by e=h/p where h is the Planck constant and p is the momentum.[49] For the 51GeV electron above,
the wavelength is about 2.41017m, small enough to explore structures well below the size of an atomic
nucleus.[134]
119
Electron
120
Formation
The Big Bang theory is the most widely accepted scientific theory to
explain the early stages in the evolution of the Universe.[135] For the
first millisecond of the Big Bang, the temperatures were over
10billionkelvins and photons had mean energies over a million
electronvolts. These photons were sufficiently energetic that they could
react with each other to form pairs of electrons and positrons.
Likewise, positron-electron pairs annihilated each other and emitted
energetic photons:
+ e+ + e
Electron
121
At the end of its lifetime, a star with more than
about 20 solar masses can undergo gravitational
collapse to form a black hole.[145] According to
classical physics, these massive stellar objects
exert a gravitational attraction that is strong
enough
to
prevent
anything,
even
electromagnetic radiation, from escaping past the
Schwarzschild radius. However, it is believed
that quantum mechanical effects may allow
Hawking radiation to be emitted at this distance.
Electrons (and positrons) are thought to be
created at the event horizon of these stellar
remnants.
Cosmic rays are particles traveling through space with high energies. Energy events as high as 3.01020eV have
been recorded.[148] When these particles collide with nucleons in the Earth's atmosphere, a shower of particles is
generated, including pions.[149] More than half of the cosmic radiation observed from the Earth's surface consists of
muons. The particle called a muon is a lepton which is produced in the upper atmosphere by the decay of a pion.
+
A muon, in turn, can decay to form an electron or positron.[150]
e + e +
Observation
Remote observation of electrons requires detection of their radiated
energy. For example, in high-energy environments such as the corona
of a star, free electrons form a plasma that radiates energy due to
Bremsstrahlung. Electron gas can undergo plasma oscillation, which is
waves caused by synchronized variations in electron density, and these
produce energy emissions that can be detected by using radio
telescopes.[152]
The frequency of a photon is proportional to its energy. As a bound
Aurorae are mostly caused by energetic electrons
[151]
electron transitions between different energy levels of an atom, it will
precipitating into the atmosphere.
absorb or emit photons at characteristic frequencies. For instance,
when atoms are irradiated by a source with a broad spectrum, distinct absorption lines will appear in the spectrum of
transmitted radiation. Each element or molecule displays a characteristic set of spectral lines, such as the hydrogen
spectral series. Spectroscopic measurements of the strength and width of these lines allow the composition and
physical properties of a substance to be determined.[153] [154]
Electron
122
In laboratory conditions, the interactions of individual electrons can be observed by means of particle detectors,
which allow measurement of specific properties such as energy, spin and charge.[112] The development of the Paul
trap and Penning trap allows charged particles to be contained within a small region for long durations. This enables
precise measurements of the particle properties. For example, in one instance a Penning trap was used to contain a
single electron for a period of 10 months.[155] The magnetic moment of the electron was measured to a precision of
eleven digits, which, in 1980, was a greater accuracy than for any other physical constant.[156]
The first video images of an electron's energy distribution were captured by a team at Lund University in Sweden,
February 2008. The scientists used extremely short flashes of light, called attosecond pulses, which allowed an
electron's motion to be observed for the first time.[157] [158]
The distribution of the electrons in solid materials can be visualized by angle resolved photoemission spectroscopy
(ARPES). This technique employs the photoelectric effect to measure the reciprocal spacea mathematical
representation of periodic structures that is used to infer the original structure. ARPES can be used to determine the
direction, speed and scattering of electrons within the material.[159]
Plasma applications
Particle beams
Electron beams are used in welding,[161] which allows energy densities
up to 107Wcm2 across a narrow focus diameter of 0.11.3 mm
and usually does not require a filler material. This welding technique
must be performed in a vacuum, so that the electron beam does not
interact with the gas prior to reaching the target, and it can be used to
join conductive materials that would otherwise be considered
unsuitable for welding.[162] [163]
Electron beam lithography (EBL) is a method of etching
semiconductors at resolutions smaller than a micron.[164] This
technique is limited by high costs, slow performance, the need to
operate the beam in the vacuum and the tendency of the electrons to
scatter in solids. The last problem limits the resolution to about 10nm.
For this reason, EBL is primarily used for the production of small
numbers of specialized integrated circuits.[165]
Electron beam processing is used to irradiate materials in order to change their physical properties or sterilize
medical and food products.[166] In radiation therapy, electron beams are generated by linear accelerators for
treatment of superficial tumors. Because an electron beam only penetrates to a limited depth before being absorbed,
typically up to 5cm for electron energies in the range 520MeV, electron therapy is useful for treating skin lesions
such as basal cell carcinomas. An electron beam can be used to supplement the treatment of areas that have been
irradiated by X-rays.[167] [168]
Particle accelerators use electric fields to propel electrons and their antiparticles to high energies. As these particles
pass through magnetic fields, they emit synchrotron radiation. The intensity of this radiation is spin dependent,
which causes polarization of the electron beama process known as the SokolovTernov effect.[169] The polarized
electron beams can be useful for various experiments. Synchrotron radiation can also be used for cooling the electron
beams, which reduces the momentum spread of the particles. Once the particles have accelerated to the required
energies, separate electron and positron beams are brought into collision. The resulting energy emissions are
observed with particle detectors and are studied in particle physics.[170]
Electron
Imaging
Low-energy electron diffraction (LEED) is a method of bombarding a crystalline material with a collimated beam of
electrons, then observing the resulting diffraction patterns to determine the structure of the material. The required
energy of the electrons is typically in the range 20200eV.[171] The reflection high energy electron diffraction
(RHEED) technique uses the reflection of a beam of electrons fired at various low angles to characterize the surface
of crystalline materials. The beam energy is typically in the range 820keV and the angle of incidence is 14.[172]
[173]
The electron microscope directs a focused beam of electrons at a specimen. As the beam interacts with the material,
some electrons change their properties, such as movement direction, angle, relative phase and energy. By recording
these changes in the electron beam, microscopists can produce atomically resolved image of the material.[174] In blue
light, conventional optical microscopes have a diffraction-limited resolution of about 200nm.[175] By comparison,
electron microscopes are limited by the de Broglie wavelength of the electron. This wavelength, for example, is
equal to 0.0037nm for electrons accelerated across a 100,000-volt potential.[176] The Transmission Electron
Aberration-corrected Microscope is capable of sub-0.05nm resolution, which is more than enough to resolve
individual atoms.[177] This capability makes the electron microscope a useful laboratory instrument for high
resolution imaging. However, electron microscopes are expensive instruments that are costly to maintain.
There are two main types of electron microscopes: transmission and scanning. Transmission electron microscopes
function in a manner similar to overhead projector, with a beam of electrons passing through a slice of material then
being projected by lenses on a photographic slide or a charge-coupled device. In scanning electron microscopes, the
image is produced by rastering a finely focused electron beam, as in a TV set, across the studied sample. The
magnifications range from 100 to 1,000,000 or higher for both microscope types. The scanning tunneling
microscope uses quantum tunneling of electrons from a sharp metal tip into the studied material and can produce
atomically resolved images of its surface.[178] [179] [180]
Other
In the free electron laser (FEL), a relativistic electron beam is passed through a pair of undulators containing arrays
of dipole magnets, whose fields are oriented in alternating directions. The electrons emit synchrotron radiation,
which, in turn, coherently interacts with the same electrons. This leads to the strong amplification of the radiation
field at the resonance frequency. FEL can emit a coherent high-brilliance electromagnetic radiation with a wide
range of frequencies, from microwaves to soft X-rays. These devices can be used in the future for manufacturing,
communication and various medical applications, such as soft tissue surgery.[181]
Electrons are at the heart of cathode ray tubes, which are used extensively as display devices in laboratory
instruments, computer monitors and television sets.[182] In a photomultiplier tube, every photon striking the
photocathode initiates an avalanche of electrons that produces a detectable current pulse.[183] Vacuum tubes use the
flow of electrons to manipulate electrical signals, and they played a critical role in the development of electronics
technology. However, they have been largely supplanted by solid-state devices such as the transistor.[184]
123
Electron
Notes
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130
Chemical element
Chemical element
A chemical element is a pure
chemical substance consisting of one
type of atom distinguished by its
atomic number, which is the number of
protons in its nucleus.[1] Familiar
examples of elements include carbon,
oxygen, aluminum, iron, copper, gold,
mercury, and lead.
As of November 2011, 118 elements
have been identified, the latest being
ununoctium in 2002.[2] Of the 118
known elements, only the first 94 are
The periodic table of the chemical elements
known to occur naturally on Earth (88
in non-trace amounts). Of these, 80 are stable or essentially so, while the others are radioactive, decaying into lighter
elements over various timescales from fractions of a second to billions of years. Additional elements, of higher
atomic numbers than those naturally occurring, have been produced artificially as the synthetic products of
man-made nuclear reactions.
Hydrogen and helium are by far the most abundant elements in the universe. However, iron is the most abundant
element (by mass) making up the Earth, and oxygen is the most common element in the Earth's crust.[3] Although all
known chemical matter is composed of these elements, chemical matter itself constitutes only about 15% of the
matter in the universe. The remainder is dark matter, a mysterious substance which is not composed of chemical
elements since it lacks protons, neutrons or electrons.
The chemical elements are thought to have been produced by various cosmic processes, including hydrogen, helium
(and smaller amounts of lithium, beryllium and boron) created during the Big Bang and cosmic-ray spallation.
Production of heavier elements, from carbon to the very heaviest elements, proceeds by stellar nucleosynthesis, and
these were made available for later solar system and planetary formation by supernovae, which blast these elements
into space.[4] The high abundance of oxygen, silicon, and iron on Earth reflect their common production in such
stars, after the lighter gaseous elements and their compounds have been subtracted. While most elements are
generally viewed as stable, a small amount of natural transformation of one element to another also occurs in the
present time, through decay of radioactive elements as well as other natural nuclear processes.
Relatively pure samples of isolated elements are uncommon in nature. While all of the 94 naturally occurring
elements have been identified in mineral samples from the Earth's crust, only a small minority of elements are found
as recognizable, relative pure minerals. Among the more common of such "native elements" are copper, silver, gold,
carbon (as coal, graphite, or diamonds), sulfur, and mercury. All but a few of the most inert elements, such as noble
gases and noble metals, are usually found on Earth in chemically combined form, as chemical compounds. While
about 32 of the chemical elements occur on Earth in native uncombined form, most of these occur as mixtures. For
example, atmospheric air is primarily a mixture of nitrogen, oxygen, and argon, and native solid elements occur in
alloys, such as that of iron and nickel.
When two distinct elements are chemically combined, with the atoms held together by chemical bonds, the result is
termed a chemical compound. Two thirds of the chemical elements occur on Earth only as compounds, and in the
remaining third, often the compound forms of the element are most common. Chemical compounds may be
composed of elements combined in exact whole-number ratios of atoms, as in water, table salt, and minerals as
quartz, calcite, and some ores. However, chemical bonding of many types of elements results in crystalline solids
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Chemical element
and metallic alloys for which exact chemical formulas do not exist. Most of the solid substance of the Earth is of this
latter type. The substances that form Earth's crust, mantle, and core do not have precise chemical empirical formulas.
The history of discovery and use of the elements began with primitive human societies that found native elements
like copper and gold, and extracted (smelted) iron and a few other metals from their ores. Alchemists and chemists
subsequently identified many more, with nearly all of the naturally-occurring elements known by 1900. The
properties of the chemical elements are often summarized using the periodic table that organizes the elements by
increasing atomic number into rows ("periods") in which the columns ("groups") share recurring ("periodic")
physical and chemical properties. Either in its pure forms, or in various chemical compounds or mixtures, almost
every element has at least one important human use. Save for short half-lived radioactive elements, all of the
elements are available industrially, most to high degrees of purity.
Around two dozen of the elements are essential to various kinds of biological life. Most rare elements on Earth are
not needed by life (exceptions being selenium and iodine), while a few quite common ones (aluminum and titanium)
are not used. Most organisms share element needs, with a few differences. For example, ocean algae use bromine but
land plants and animals seem to need none, and all animals require sodium, but some plants do not. Just six
elementscarbon, hydrogen, nitrogen, oxygen, calcium, and phosphorusmake up almost 99% of the mass of a
human body (see composition of the human body for a complete list). In addition to the six major elements that
compose most of the human body, humans require consumption of at least a dozen more elements in the form of
certain chemical compounds.
Description
The lightest of the chemical elements are hydrogen and helium, both created by Big Bang nucleosynthesis during the
first 20 minutes of the universe[5] in a ratio of around 3:1 by mass (approximately 12:1 by number of atoms). Almost
all other elements found in nature, including some further hydrogen and helium created since then, were made by
various natural or (at times) artificial methods of nucleosynthesis. On Earth, small amounts of new atoms are
naturally produced in nucleogenic reactions, or in cosmogenic processes, such as cosmic ray spallation. New atoms
are also naturally produced on Earth as radiogenic daughter isotopes of ongoing radioactive decay processes such as
alpha decay, beta decay, spontaneous fission, cluster decay, and other rarer modes of decay.
Of the 94 naturally occurring elements, those with atomic numbers 1 through 40 are all considered to be stable
isotopes. Elements with atomic numbers 41 through 82 are apparently stable (except technetium, element 43 and
promethium, element 61) but theoretically unstable, and thus possibly mildly radioactive. The half-lives of elements
41 through 82 are so long however that their radioactive decay has yet to be detected by experiment. These
"theoretical radionuclides" have half-lives at least 100 million times longer than the estimated age of the universe.
Elements with atomic numbers 83 through 94 are unstable to the point that their radioactive decay can be detected.
Some of these elements, notably thorium (atomic number 90) and uranium (atomic number 92), have one or more
isotopes with half-lives long enough to survive as remnants of the explosive stellar nucleosynthesis that produced the
heavy elements before the formation of our solar system. For example, at over 1.91019 years, over a billion times
longer than the current estimated age of the universe, bismuth-209 (atomic number 83) has the longest known alpha
decay half-life of any naturally occurring element.[6] [7] The very heaviest elements (those beyond plutonium, atomic
number 94) undergo radioactive decay with half-lives so short that they have only been observed as the result of
experimental observation.
As of 2010, there are 118 known elements (in this context, "known" means observed well-enough, even from just a
few decay products, to have been differentiated from any other element).[8] [9] Of these 118 elements, 94 occur
naturally on Earth. Six of these occur in extreme trace quantities: technetium, atomic number 43; promethium,
number 61; astatine, number 85; francium, number 87; neptunium, number 93; and plutonium, number 94. These 94
elements have been detected in the universe at large, in the spectra of stars and also supernovae, where short-lived
radioactive elements are newly being made. The first 94 elements have been detected directly on Earth as primordial
132
Chemical element
nuclides present from the formation of the solar system, or as naturally-occurring fission or transmutation products
of uranium and thorium.
The remaining 24 heavier elements, not found today either on Earth or in astronomical spectra, have been derived
artificially. All of the heavy elements that are derived solely through artificial means are radioactive, with very short
half-lives; if any atoms of these elements were present at the formation of Earth, they are extremely likely to have
already decayed, and if present in novae, have been in quantities too small to have been noted. Technetium was the
first purportedly non-naturally occurring element to be synthesized, in 1937, although trace amounts of technetium
have since been found in nature (and also the element may have been discovered naturally in 1925). This pattern of
artificial production and later natural discovery has been repeated with several other radioactive naturally-occurring
rare elements.
Lists of the elements are available by name, by symbol, by atomic number, by density, by melting point, and by
boiling point as well as Ionization energies of the elements. The nuclides of stable and radioactive elements are also
available as a list of nuclides, sorted by length of half-life for those that are unstable. One of the most convenient,
and certainly the most traditional presentation of the elements, is in form of periodic table, which groups elements
with similar chemical properties (and usually also similar electronic structures) together.
Atomic number
The atomic number of an element is equal to the number of protons that defines the element. For example, all carbon
atoms contain 6 protons in their nucleus; so the atomic number of carbon is 6. Carbon atoms may have different
numbers of neutrons; atoms of the same element having different numbers of neutrons are known as isotopes of the
element.
The number of protons in the atomic nucleus also determines its electric charge, which in turn determines the
number of electrons of the atom in its non-ionized state. The electrons are placed into atomic orbitals which
determine the atom's various chemical properties. The number of neutrons in a nucleus usually has very little effect
on an elements' chemical properties (except in the case of hydrogen and deuterium). Thus, all carbon isotopes have
nearly identical chemical properties because they all have six protons and six electrons, even though carbon atoms
may differ in number of neutrons. It is for this reason that atomic number rather than mass number or atomic weight
is considered the identifying characteristic of a chemical element. The symbol for atomic number is Z.
133
Chemical element
abundance, relative to the atomic mass unit (u). This number may be a fraction that is not close to a whole number,
due to the averaging process. For example, the relative atomic mass of chlorine is 35.453 u, which differs greatly
from a whole number due to being made of an average of 76% chlorine-35 and 24% chlorine-37. Whenever a
relative atomic mass value differs by more than 1% from a whole number, it is due to this averaging effect resulting
from significant amounts of more than one isotope being naturally present in the sample of the element in question.
Isotopes
Isotopes are atoms of the same element (that is, with the same number of protons in their atomic nucleus), but having
different numbers of neutrons. Most (66 of 94) naturally occurring elements have more than one stable isotope. Thus,
for example, there are three main isotopes of carbon. All carbon atoms have 6 protons in the nucleus, but they can
have either 6, 7, or 8 neutrons. Since the mass numbers of these are 12, 13 and 14 respectively, the three isotopes of
carbon are known as carbon-12, carbon-13, and carbon-14, often abbreviated to 12C, 13C, and 14C. Carbon in
everyday life and in chemistry is a mixture of 12C, 13C, and (a very small fraction of) 14C atoms.
Except in the case of the isotopes of hydrogen (which differ greatly from each other in relative massenough to
cause chemical effects), the isotopes of the various elements are typically chemically nearly indistinguishable from
each other. For example, the three naturally-occurring isotopes of carbon have essentially the same chemical
properties, but different nuclear properties. In this example, carbon-12 and carbon-13 are stable atoms, but carbon-14
is unstable; it is radioactive, undergoing beta decay into nitrogen-14.
All of the elements have some isotopes that are radioactive (radioisotopes), although not all of these radioisotopes
occur naturally. The radioisotopes typically decay into other elements upon radiating an alpha or beta particle. If an
element has isotopes that are not radioactive, they are termed "stable." All of the known stable isotopes occur
naturally (see primordial isotope). The many radioisotopes that are not found in nature have been characterized from
being artificially made. Certain elements have no stable isotopes and are composed only of radioactive isotopes:
specifically the elements without any stable isotopes are technetium (atomic number 43), promethium (atomic
number 61), and all observed elements with atomic numbers greater than 82.
Of the 80 elements with at least one stable isotope, 26 have only one stable isotope, and the mean number of stable
isotopes for the 80 stable elements is 3.1 stable isotopes per element. The largest number of stable isotopes that occur
for an element is 10 (for tin, element 50).
Allotropes
Atoms of pure elements may bond to each other chemically in more than one way, allowing the pure element to exist
in multiple structures (spacial arrangements of atoms), known as allotropes, which differ in their properties. For
example, carbon can be found as diamond, which has a tetrahedral structure around each carbon atom; graphite,
which has layers of carbon atoms with a hexagonal structure stacked on top of each other; graphene, which is a
single layer of graphite that is incredibly strong; fullerenes, which have nearly spherical shapes; and carbon
nanotubes, which are tubes with a hexagonal structure (even these may differ from each other in electrical
properties). The ability for an element to exist in one of many structural forms is known as 'allotropy'.
The standard state, or reference state, of an element is defined as its thermodynamically most stable state at 1 bar at a
given temperature (typically at 298.15 K). In thermochemistry, an element is defined to have an enthalpy of
formation of zero in its standard state. For example, the reference state for carbon is graphite, because it is more
stable than the other allotropes.
134
Chemical element
Properties
Several kinds of descriptive categorizations can be applied broadly to the elements, including consideration of their
general physical and chemical properties, their states of matter under familiar conditions, their melting and boiling
points, their densities, their crystal structures as solids, and their origins.
General properties
Several terms are commonly used to characterize the general physical and chemical properties of the chemical
elements. A first distinction is between the metals, which readily conduct electricity, and the nonmetals, which do
not, with a small group (the metalloids) having intermediate properties, often behaving as semiconductors.
A more refined classification is often shown in colored presentations of the periodic table; this system restricts the
terms "metal" and "nonmetal" to only certain of the more broadly defined metals and nonmetals, adding additional
terms for certain sets of the more broadly viewed metals and nonmetals. The version of this classification used in the
periodic tables presented here includes: actinides, alkali metals, alkaline earth metals, halogens, lanthanides,
metals (or "other metals"), metalloids, noble gases, nonmetals (or "other nonmetals"), and transition metals. In
this system, the alkali metals, alkaline earth metals, and transition metals, as well as the lanthanides and the
actinides, are special groups of the metals viewed in a broader sense. Similarly, the halogens and the noble gases are
nonmetals, viewed in the broader sense. In some presentations, the halogens are not distinguished, with astatine
identified as a metalloid and the others identified as nonmetals.
States of matter
Another commonly used basic distinction among the elements is their state of matter (phase), solid, liquid, or gas, at
a selected standard temperature and pressure (STP). Most of the elements are solids at conventional temperatures and
atmospheric pressure, while several are gases. Only bromine and mercury are liquids at 0 degrees Celsius (32
degrees Fahrenheit) and normal atmospheric pressure; caesium and gallium are solids at that temperature, but melt at
28.4 C (83.2 F) and 29.8 C (85.6 F), respectively.
Melting and boiling points
Melting and boiling points, typically expressed in degrees Celsius at a pressure of one atmosphere, are commonly
used in characterizing the various elements. While known for most elements, either or both of these measurements is
still undetermined for some of the radioactive elements available in only tiny quantities. Since helium remains a
liquid even at absolute zero at atmospheric pressure, it has only a boiling point, and not a melting point, in
conventional presentations.
Densities
The density at a selected standard temperature and pressure (STP) is frequently used in characterizing the elements.
Density is often expressed in grams per cubic centimeter (g/cm3). Since several elements are gases at commonly
encountered temperatures, their densities are usually stated for their gaseous forms; when liquefied or solidified, the
gaseous elements have densities similar to those of the other elements.
When an element has allotropes with different densities, one representative allotrope is typically selected in
summary presentations, while densities for each allotrope can be stated where more detail is provided. For example,
the three familiar allotropes of carbon (amorphous carbon, graphite, and diamond) have densities of 1.82.1, 2.267,
and 3.515 g/cm3, respectively.
135
Chemical element
Crystal structures
The elements studied to date as solid samples have eight kinds of crystal structures: cubic, body-centered cubic,
face-centered cubic, hexagonal, monoclinic, orthorhombic, rhombohedral, and tetragonal. For some of the
synthetically produced transuranic elements, available samples have been too small to determine crystal structures.
Occurrence and origin on Earth
Checmical elements may also be categorized by their origin on Earth, with the first 94 considered to be naturally
occurring, while those with atomic numbers beyond 94 have only been produced artificially as the synthetic products
of man-made nuclear reactions.
Of the 94 naturally occurring elements, 84 are considered to be primordial and either stable or metastable
(apparently stable but theoretically unstable, or radioactive). The remaining 10 naturally occurring elements possess
half lives too short for them to have been present at the beginning of the Solar System, and are therefore considered
to be transient elements. Of these 10 transient elements, 7 (polonium, astatine, radon, francium, radium, actinium,
and protactinium) are relatively common decay products of thorium, uranium, and plutonium. The remaining 3
transient elements (technetium, promethium, and neptunium) occur only rarely, as products of rare nuclear reaction
processes from uranium or other heavy elements.
Elements with atomic numbers 1 through 40 are all stable, while those with atomic numbers 41 through 82 (except
technetium and promethium) are metastable. The half-lives of these metastable "theoretical radionuclides" are so
long (at least 100 million times longer than the estimated age of the universe) that their radioactive decay has yet to
be detected by experiment. Elements with atomic numbers 83 through 94 are unstable to the point that their
radioactive decay can be detected. Some of these elements, notably thorium (atomic number 90) and uranium
(atomic number 92), have one or more isotopes with half-lives long enough to survive as remnants of the explosive
stellar nucleosynthesis that produced the heavy elements before the formation of our Solar System. For example, at
over 1.91019 years, over a billion times longer than the current estimated age of the universe, bismuth-209 (atomic
number 83) has the longest known alpha decay half-life of any naturally occurring element.[6] [7] The very heaviest
elements (those beyond plutonium, atomic number 94) undergo radioactive decay with half-lives so short that they
have only been observed as the result of experimental observation.
136
Chemical element
Atomic numbers
The known elements have atomic numbers from 1 through 118, conventionally presented as Arabic numerals. Since
the elements can be uniquely sequenced by atomic number, conventionally from lowest to hightest (as in a periodic
table), sets of elements are sometimes specified by such notation as "through", "beyond", or "from ... through", as in
"through iron", "beyond uranium", or "from lanthanum through lutetium". The terms "light" and "heavy" are
sometimes also used informally to indicate relative atomic numbers (not densities!), as in "lighter than carbon" or
"heavier than lead", although technically the weight or mass of atoms of an element (their atomic weights or atomic
masses) do not always increase monotonically with their atomic numbers.
Element names
The naming of various substances now known as elements precedes the atomic theory of matter, as names were
given locally by various cultures to various minerals, metals, compounds, alloys, mixtures, and other materials,
although at the time it was not known which chemicals were elements and which compounds. As they were
identified as elements, the existing names for anciently-known elements (e.g., gold, mercury, iron) were kept in most
countries. National differences emerged over the names of elements either for convenience, linguistic niceties, or
nationalism. For a few illustrative examples: German speakers use "Wasserstoff" (water substance) for "hydrogen",
"Sauerstoff" (acid substance) for "oxygen" and "Stickstoff" (smothering substance) for "nitrogen", while English and
some romance languages use "sodium" for "natrium" and "potassium" for "kalium", and the French, Italians, Greeks,
Portuguese and Poles prefer "azote/azot/azoto" (from roots meaning "no life") for "nitrogen".
For purposes of international communication and trade, the official names of the chemical elements both ancient and
more recently recognized are decided by the International Union of Pure and Applied Chemistry (IUPAC), which
has decided on a sort of international English language, drawing on traditional English names even when an
element's chemical symbol is based on a Latin or other traditional word, for example adopting "gold" rather than
"aurum" as the name for the 79th element (Au). IUPAC prefers the British spellings "aluminium" and "caesium"
over the U.S. spellings "aluminum" and "cesium", and the U.S. "sulfur" over the British "sulphur". However,
elements that are practical to sell in bulk in many countries often still have locally used national names, and
countries whose national language does not use the Latin alphabet are likely to use the IUPAC element names.
According to IUPAC, chemical elements are not proper nouns in English; consequently, the full name of an element
is not routinely capitalized in English, even if derived from a proper noun, as in californium and einsteinium. Isotope
names of chemical elements are also uncapitalized if written out, e.g., carbon-12 or uranium-235. Chemical element
symbols are always capitalized (see below).
In the second half of the twentieth century, physics laboratories became able to produce nuclei of chemical elements
with half-lives too short for an appreciable amount of them to exist at any time. These are also named by IUPAC,
which generally adopts the name chosen by the discoverer. This practice can lead to the controversial question of
which research group actually discovered an element, a question that has delayed naming of elements with atomic
number of 104 and higher for a considerable time. (See element naming controversy).
Precursors of such controversies involved the nationalistic namings of elements in the late 19th century. For
example, lutetium was named in reference to Paris, France. The Germans were reluctant to relinquish naming rights
to the French, often calling it cassiopeium. Similarly, the British discoverer of niobium originally named it
columbium, in reference to the New World. It was used extensively as such by American publications prior to
international standardization.
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Chemical element
Chemical symbols
Specific chemical elements
Before chemistry became a science, alchemists had designed arcane symbols for both metals and common
compounds. These were however used as abbreviations in diagrams or procedures; there was no concept of atoms
combining to form molecules. With his advances in the atomic theory of matter, John Dalton devised his own
simpler symbols, based on circles, which were to be used to depict molecules.
The current system of chemical notation was invented by Berzelius. In this typographical system chemical symbols
are not used as mere abbreviations though each consists of letters of the Latin alphabet they are symbols
intended to be used by peoples of all languages and alphabets. The first of these symbols were intended to be fully
universal; since Latin was the common language of science at that time, they were abbreviations based on the Latin
names of metals Cu comes from Cuprum, Fe comes from Ferrum, Ag from Argentum. The symbols were not
followed by a period (full stop) as abbreviations were. Later chemical elements were also assigned unique chemical
symbols, based on the name of the element, but not necessarily in English. For example, sodium has the chemical
symbol 'Na' after the Latin natrium. The same applies to "W" (wolfram) for tungsten, "Fe" (ferrum) for iron, "Hg"
(hydrargyrum) for mercury, "Sn" (stannum) for tin, "K" (kalium) for potassium, "Au" (aurum) for gold, "Ag"
(argentum) for silver, "Pb" (plumbum) for lead, "Cu" (Cuprum) for copper, and "Sb" (stibium) for antimony.
Chemical symbols are understood internationally when element names might need to be translated. There are
sometimes differences; for example, the Germans have used "J" instead of "I" for iodine, so the character would not
be confused with a Roman numeral.
The first letter of a chemical symbol is always capitalized, as in the preceding examples, and the subsequent letters,
if any, are always lower case (small letters). Thus, the symbols for californium or einsteinium are Cf and Es.
General chemical symbols
There are also symbols for series of chemical elements, for comparative formulas. These are one capital letter in
length, and the letters are reserved so they are not permitted to be given for the names of specific elements. For
example, an "X" is used to indicate a variable group amongst a class of compounds (though usually a halogen), while
"R" is used for a radical, meaning a compound structure such as a hydrocarbon chain. The letter "Q" is reserved for
"heat" in a chemical reaction. "Y" is also often used as a general chemical symbol, although it is also the symbol of
yttrium. "Z" is also frequently used as a general variable group. "L" is used to represent a general ligand in inorganic
and organometallic chemistry. "M" is also often used in place of a general metal. At least one additional, two-letter
generic chemical symbol is also in informal usage, "Ln" for any lanthanide element.
Isotope symbols
Isotopes are distinguished by the atomic mass number (total protons and neutrons) for a particular isotope of an
element, with this number combined with the pertinent element's symbol. IUPAC prefers that isotope symbols be
written in superscript notation when practical, for example 12C and 235U. However, other notations, such as
carbon-12 and uranium-235, or C-12 and U-235, are also used.
As a special case, the three naturally occurring isotopes of the element hydrogen are often specified as H for 1H
(protium), D for 2H (deuterium), and T for 3H (tritium). This convention is easier to use in chemical equations,
replacing the need to write out the mass number for each atom. For example, the formula for heavy water may be
written D2O instead of 2H2O.
138
Chemical element
139
During the early phases of the Big Bang, nucleosynthesis of hydrogen nuclei resulted in the production of
hydrogen-1 (protonium, 1H) and helium-4 (4He), as well as a smaller amount of deuterium (2H) and very minuscule
amounts (on the order of 1010) of lithium and beryllium. Even smaller amounts of boron may have been produced
in the Big Bang, since it has been observed in some very old stars, while carbon has not.[10] It is generally agreed
that no heavier elements than boron were produced in the Big Bang. As a result, the primordial abundance of atoms
(or ions) consisted of roughly 75% 1H, 25% 4He, and 0.01% deuterium, with only tiny traces of lithium, beryllium,
and perhaps boron.[11] Subsequent enrichment of galactic halos occurred due to stellar nucleosynthesis and
supernova nucleosynthesis.[12] However, the element abundance in intergalactic space can still closely resemble
primordial conditions, unless it has been enriched by some means.
On Earth (and elsewhere), trace amounts of various elements continue to be produced from other elements as
products of natural transmutation processes. These include some produced by cosmic rays or other nuclear reactions
(see cosmogenic and nucleogenic nuclides), and others produced as decay products of long-lived primordial
nuclides.[13] For example, trace (but detectable) amounts of carbon-14 (14C) are continually produced in the
atmosphere by cosmic rays impacting nitrogen atoms, and argon-40 (40Ar) is continually produced by the decay of
primordially occurring but unstable potassium-40 (40K). Also, three primordially occurring but radioactive actinides,
thorium, uranium, and plutonium, decay through a series of recurrently produced but unstable radioactive elements
such as radium and radon, which are transiently present in any sample of these metals or their ores or compounds.
Three other radioactive elements, technetium, promethium, and neptunium, occur only incidentally in natural
Chemical element
materials, produced as individual atoms by natural fission of the nuclei of various heavy elements or in other rare
nuclear processses.
Human technology has produced various additional elements beyond these first 94, with those through atomic
number 118 now known.
Abundance
The following graph (note log scale) shows abundance of elements in our solar system. The table shows the twelve
most common elements in our galaxy (estimated spectroscopically), as measured in parts per million, by mass.[14]
Nearby galaxies that have evolved along similar lines have a corresponding enrichment of elements heavier than
hydrogen and helium. The more distant galaxies are being viewed as they appeared in the past, so their abundances
of elements appear closer to the primordial mixture. As physical laws and processes appear common throughout the
visible universe, however, it is expected that these galaxies will likewise have evolved similar abundances of
elements.
The abundance of elements in the Solar System is in keeping with their origin from nucleosynthesis in the Big Bang
and a number of progenitor supernova stars. Very abundant hydrogen and helium are products of the Big Bang, but
the next three elements are rare since they had little time to form in the Big Bang and are not made in stars (they are,
however, produced in small quanties by breakup of heavier elements in interstellar dust, as a result of impact by
cosmic rays). Beginning with carbon, elements are produced in stars by buildup from alpha particles (helium nuclei),
resulting in an alternatingly-larger abundance of elements with even atomic numbers (these are also more stable). In
general, such elements up to iron are made in large stars in the process of becoming supernovas. Iron-56 is
particularly common, since it is the most stable element that can easily be made from alpha particles (being a product
of decay of radioactive nickel-56, ultimately made from 14 helium nuclei). Elements heavier than iron are made in
energy-absorbing processes in large stars, and their abundance in the universe (and on Earth) generally decreases
with their atomic number.
The abundance of the chemical elements on Earth varies from air to crust to ocean, and in various types of life. The
abundance of elements in Earth's crust differs from those in the universe (and also the Sun and heavy planets like
Jupiter) mainly in selective loss of the very lightest elements (hydrogen and helium) and also volatile neon, carbon,
nitrogen and sulfur, as a result of solar heating in the early formation of the solar system. Aluminum is also far more
common in the Earth and Earth's crust than the universe and solar system, but the composition of Earth's mantle
(which has more magnesium and iron in place of aluminum) more closely mirrors that of the universe, save for the
noted loss of volitile elements.
The composition of the human body, by contrast, more closely follows the composition of seawater, save that the
human body has additional stores of carbon and nitrogen which are necessary to form the proteins and nucleic acids
that are characteristic of living organisms. Certain kinds of organisms require particular additional elements, for
example the magnesium in chlorophyll in green plants, the calcium in mollusc shells, or the iron in the hemoglobin
in vertebrate animals' red blood cells.
140
Chemical element
141
Abundances of the chemical elements in the Solar system. Hydrogen and helium are
most common, from the Big Bang. The next three elements (Li, Be, B) are rare because
they are poorly synthesized in the Big Bang and also in stars. The two general trends in
the remaining stellar-produced elements are: (1) an alternation of abundance in elements
as they have even or odd atomic numbers, and (2) a general decrease in abundance, as
elements become heavier.
Parts per
million
by mass
Hydrogen
739,000
Helium
240,000
Oxygen
10,400
Carbon
4,600
Neon
1,340
Iron
1,090
Nitrogen
960
Silicon
650
Magnesium
580
Sulfur
440
Potassium
210
Nickel
100
He
Be
Na Mg
Al
Si
Cl Ar
Cu Zn Ga Ge
As
Se Br Kr
Ca Sc
Rb Sr
Ti
Cs Ba La
Cr Mn Fe
Co
Ni
Zr Nb Mo Tc
Ru Rh
Pd Ag Cd In
Sn
Sb
Te
Hf Ta
Pb
Bi
Po At Rn
Re
Os
Ir
Pt
Au Hg Tl
Fr Ra Ac ** Rf Db Sg
Bh
Hs
Mt
Ds
Rg
Ce Pr Nd Pm Sm Eu
** Th Pa
Ne
Gd Tb Dy Ho Er Tm Yb Lu
Np Pu Am Cm Bk Cf Es Fm Md No Lr
Xe
Chemical element
142
Quantity
elements
Essential trace
elements
History
Evolving definitions
The concept of an "element" as an
undivisible substance has developed through
three major historical phases: Classical
definitions (such as those of the ancient
Greeks), chemical definitions, and atomic
definitions.
Classical definitions
Ancient philosophy posited a set of classical
elements to explain observed patterns in
nature. These elements originally referred to
earth, water, air and fire rather than the
chemical elements of modern science.
The term 'elements' (stoicheia) was first
used by the Greek philosopher Plato in about
360 BCE, in his dialogue Timaeus, which
includes a discussion of the composition of
inorganic and organic bodies and is a
speculative treatise on chemistry. Plato
believed the elements introduced a century
earlier by Empedocles were composed of
small polyhedral forms: tetrahedron (fire),
octahedron (air), icosahedron (water), and
cube (earth).[16] [17]
Aristotle, c. 350 BCE, also used the term stoicheia and added a fifth element called aether, which formed the
heavens. Aristotle defined an element as:
Element one of those bodies into which other bodies can decompose, and that itself is not capable of being
divided into other.[18]
Chemical definitions
In 1661, Robert Boyle showed that there were more than just the four classical elements that the ancients had
assumed.[19] The first modern list of chemical elements was given in Antoine Lavoisier's 1789 Elements of
Chemistry, which contained thirty-three elements, including light and caloric.[20] By 1818, Jns Jakob Berzelius had
determined atomic weights for forty-five of the forty-nine then-accepted accepted elements. Dmitri Mendeleev had
sixty-six elements in his periodic table of 1869.
From Boyle until the early 20th century, an element was defined as a pure substance that could not be decomposed
into any simpler substance.[19] Put another way, a chemical element cannot be transformed into other chemical
elements by chemical processes. Elements during this time were generally distinguished by their atomic weights, a
Chemical element
property measurable with fair accuracy by available analytical techniques.
Atomic definitions
The 1913 discovery by Henry Moseley that the nuclear charge is the physical basis for an atom's atomic number,
further refined when the nature of protons and neutrons became appreciated, eventually led to the current definition
of an element, based on atomic number (number of protons per atomic nucleus). The use of atomic numbers, rather
than atomic weights, to distinguish elements has greater predictive value (since these numbers are integers), and also
resolves some ambiguities in the chemistry-based view due to varying properties of isotopes and allotropes within
the same element. Currently IUPAC defines an element to exist if it has isotopes with a lifetime longer than the
1014 seconds which takes the nucleus to form an electronic cloud.[21]
By 1914, seventy-two elements were known, all naturally occurring.[22] The remaining naturally occurring elements
were discovered or isolated is subsequent decades, and various additional elements have also been produced
synthetically, with much of that work pioneered by Glenn T. Seaborg. In 1955, element 101 was discovered and
named mendelevium in honor of D.I. Mendeleev, the first to arrange the elements in a periodic manner. Most
recently, the synthesis of element 118 was reported in October 2006, and the synthesis of element 117 was reported
in April 2010.[23]
Such now-familiar industrial materials as aluminum, silicon, nickel, chromium, magnesium, and tungsten
Reactive metals such as lithium, sodium, potassium, and calcium
The halogens fluorine, chlorine, bromine, and iodine
Gases such as hydrogen, oxygen, nitrogen, helium, argon, and neon
Most of the rare-earth elements, including cerium, lanthanum, gadolinium, and neodymium, and
The more common radioactive elements, including uranium, thorium, radium, and radon
143
Chemical element
144
List of elements
Atomic
no.
Name
State
at
STP
Occurrence
Description
Hydrogen
Gas
Primordial
Non-metal
Helium
He
18
Gas
Primordial
Noble gas
Lithium
Li
Solid
Primordial
Alkali metal
Beryllium
Be
Solid
Primordial
Boron
13
Solid
Primordial
Metalloid
Carbon
14
Solid
Primordial
Non-metal
Nitrogen
15
Gas
Primordial
Non-metal
Oxygen
16
Gas
Primordial
Non-metal
Fluorine
17
Gas
Primordial
Halogen
10
Neon
Ne
18
Gas
Primordial
Noble gas
11
Sodium
Na
Solid
Primordial
Alkali metal
12
Magnesium
Mg
Solid
Primordial
13
Aluminium
Al
13
Solid
Primordial
Metal
14
Silicon
Si
14
Solid
Primordial
Metalloid
15
Phosphorus
15
Solid
Primordial
Non-metal
16
Sulfur
16
Solid
Primordial
Non-metal
17
Chlorine
Cl
17
Gas
Primordial
Halogen
18
Argon
Ar
18
Gas
Primordial
Noble gas
19
Potassium
Solid
Primordial
Alkali metal
20
Calcium
Ca
Solid
Primordial
21
Scandium
Sc
Solid
Primordial
Transition metal
22
Titanium
Ti
Solid
Primordial
Transition metal
23
Vanadium
Solid
Primordial
Transition metal
Chemical element
145
24
Chromium
Cr
Solid
Primordial
Transition metal
25
Manganese
Mn
Solid
Primordial
Transition metal
26
Iron
Fe
Solid
Primordial
Transition metal
27
Cobalt
Co
Solid
Primordial
Transition metal
28
Nickel
Ni
10
Solid
Primordial
Transition metal
29
Copper
Cu
11
Solid
Primordial
Transition metal
30
Zinc
Zn
12
Solid
Primordial
Transition metal
31
Gallium
Ga
13
Solid
Primordial
Metal
32
Germanium
Ge
14
Solid
Primordial
Metalloid
33
Arsenic
As
15
Solid
Primordial
Metalloid
34
Selenium
Se
16
Solid
Primordial
Non-metal
35
Bromine
Br
17
Liquid
Primordial
Halogen
36
Krypton
Kr
18
Gas
Primordial
Noble gas
37
Rubidium
Rb
Solid
Primordial
Alkali metal
38
Strontium
Sr
Solid
Primordial
39
Yttrium
Solid
Primordial
Transition metal
40
Zirconium
Zr
Solid
Primordial
Transition metal
41
Niobium
Nb
Solid
Primordial
Transition metal
42
Molybdenum
Mo
Solid
Primordial
Transition metal
43
Technetium
Tc
Solid
Transient
Transition metal
44
Ruthenium
Ru
Solid
Primordial
Transition metal
45
Rhodium
Rh
Solid
Primordial
Transition metal
46
Palladium
Pd
10
Solid
Primordial
Transition metal
47
Silver
Ag
11
Solid
Primordial
Transition metal
48
Cadmium
Cd
12
Solid
Primordial
Transition metal
49
Indium
In
13
Solid
Primordial
Metal
50
Tin
Sn
14
Solid
Primordial
Metal
51
Antimony
Sb
15
Solid
Primordial
Metalloid
52
Tellurium
Te
16
Solid
Primordial
Metalloid
53
Iodine
17
Solid
Primordial
Halogen
54
Xenon
Xe
18
Gas
Primordial
Noble gas
55
Caesium
Cs
Solid
Primordial
Alkali metal
56
Barium
Ba
Solid
Primordial
57
Lanthanum
La
Solid
Primordial
Lanthanide
58
Cerium
Ce
Solid
Primordial
Lanthanide
59
Praseodymium
Pr
Solid
Primordial
Lanthanide
60
Neodymium
Nd
Solid
Primordial
Lanthanide
61
Promethium
Pm
Solid
Transient
Lanthanide
62
Samarium
Sm
Solid
Primordial
Lanthanide
Chemical element
146
63
Europium
Eu
Solid
Primordial
Lanthanide
64
Gadolinium
Gd
Solid
Primordial
Lanthanide
65
Terbium
Tb
Solid
Primordial
Lanthanide
66
Dysprosium
Dy
Solid
Primordial
Lanthanide
67
Holmium
Ho
Solid
Primordial
Lanthanide
68
Erbium
Er
Solid
Primordial
Lanthanide
69
Thulium
Tm
Solid
Primordial
Lanthanide
70
Ytterbium
Yb
Solid
Primordial
Lanthanide
71
Lutetium
Lu
Solid
Primordial
Lanthanide
72
Hafnium
Hf
Solid
Primordial
Transition metal
73
Tantalum
Ta
Solid
Primordial
Transition metal
74
Tungsten
Solid
Primordial
Transition metal
75
Rhenium
Re
Solid
Primordial
Transition metal
76
Osmium
Os
Solid
Primordial
Transition metal
77
Iridium
Ir
Solid
Primordial
Transition metal
78
Platinum
Pt
10
Solid
Primordial
Transition metal
79
Gold
Au
11
Solid
Primordial
Transition metal
80
Mercury
Hg
12
Liquid
Primordial
Transition metal
81
Thallium
Tl
13
Solid
Primordial
Metal
82
Lead
Pb
14
Solid
Primordial
Metal
83
Bismuth
Bi
15
Solid
Primordial
Metal
84
Polonium
Po
16
Solid
Transient
Metalloid
85
Astatine
At
17
Solid
Transient
Halogen
86
Radon
Rn
18
Gas
Transient
Noble gas
87
Francium
Fr
Solid
Transient
Alkali metal
88
Radium
Ra
Solid
Transient
89
Actinium
Ac
Solid
Transient
Actinide
90
Thorium
Th
Solid
Primordial
Actinide
91
Protactinium
Pa
Solid
Transient
Actinide
92
Uranium
Solid
Primordial
Actinide
93
Neptunium
Np
Solid
Transient
Actinide
94
Plutonium
Pu
Solid
Primordial
Actinide
95
Americium
Am
Solid
Synthetic
Actinide
96
Curium
Cm
Solid
Synthetic
Actinide
97
Berkelium
Bk
Solid
Synthetic
Actinide
98
Californium
Cf
Solid
Synthetic
Actinide
99
Einsteinium
Es
Solid
Synthetic
Actinide
100
Fermium
Fm
Solid
Synthetic
Actinide
101
Mendelevium
Md
Solid
Synthetic
Actinide
Chemical element
147
102
Nobelium
No
Solid
Synthetic
Actinide
103
Lawrencium
Lr
Solid
Synthetic
Actinide
104
Rutherfordium
Rf
Synthetic
Transition metal
105
Dubnium
Db
Synthetic
Transition metal
106
Seaborgium
Sg
Synthetic
Transition metal
107
Bohrium
Bh
Synthetic
Transition metal
108
Hassium
Hs
Synthetic
Transition metal
109
Meitnerium
Mt
Synthetic
110
Darmstadtium
Ds
10
Synthetic
111
Roentgenium
Rg
11
Synthetic
112
Copernicium
Cn
12
Synthetic
113
(Ununtrium)
Uut
13
Synthetic
114
(Ununquadium) Uuq
14
Synthetic
115
(Ununpentium) Uup
15
Synthetic
116
(Ununhexium)
Uuh
16
Synthetic
117
(Ununseptium)
Uus
17
Synthetic
118
(Ununoctium)
Uuo
18
Synthetic
Transition metal
References
[1] IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006) " chemical element
(http:/ / goldbook. iupac. org/ C01022. html)".
[2] Oganessian, YT (2007). "Heaviest nuclei from 48Ca-induced reactions" (http:/ / www. icpress. co. uk/ etextbook/ p573/ p573_chap01. pdf).
Journal of Physics G: Nuclear and Particle Physics 34 (4): R165R242. Bibcode2007JPhG...34..165O. doi:10.1088/0954-3899/34/4/R01. .
Retrieved 2011-05-07.
[3] Los Alamos National Laboratory (2011). "Periodic Table of Elements: Oxygen" (http:/ / periodic. lanl. gov/ 8. shtml). Los Alamos, New
Mexico: Los Alamos National Security, LLC. . Retrieved 2011-05-07.
[4] E. M. Burbidge, G. R. Burbidge, W. A. Fowler, F. Hoyle (1957). "Synthesis of the Elements in Stars". Reviews of Modern Physics 29 (4):
547650. Bibcode1957RvMP...29..547B. doi:10.1103/RevModPhys.29.547.
[5] See the timeline on p.10 of Gaitskell, R; et al. (2006). "Evidence for Dark Matter" (http:/ / gaitskell. brown. edu/ physics/ talks/
0408_SLAC_SummerSchool/ Gaitskell_DMEvidence_v16. pdf). Physical Review C 74 (4): 044602. Bibcode2006PhRvC..74d4602O.
doi:10.1103/PhysRevC.74.044602. .
[6] Dum, B (2003-04-23). "Bismuth breaks half-life record for alpha decay" (http:/ / physicsweb. org/ articles/ news/ 7/ 4/ 16).
Physicsworld.com (Bristol, England: Institute of Physics). . Retrieved 2011-05-07.
[7] de Marcillac, P; Coron N, Dambier G, Leblanc J, and Moalic J-P (2003). "Experimental detection of alpha-particles from the radioactive
decay of natural bismuth". Nature 422 (6934): 8768. Bibcode2003Natur.422..876D. doi:10.1038/nature01541. PMID12712201.
[8] Sanderson, K (17 October 2006). "Heaviest element made again" (http:/ / www. nature. com/ news/ 2006/ 061016/ full/ 061016-4. html).
Nature News. doi:10.1038/news061016-4. .
[9] Schewe, P; Stein, B (17 October 200). "Elements 116 and 118 Are Discovered" (http:/ / www. aip. org/ pnu/ 2006/ 797. html). Physics News
Update. American Institute of Physics. . Retrieved 2006-10-19.
[10] Wilford, JN (14 January 1992). "Hubble Observations Bring Some Surprises" (http:/ / query. nytimes. com/ gst/ fullpage.
html?res=9E0CE5D91F3AF937A25752C0A964958260). New York Times. .
[11] Wright, EL (12 September 2004). "Big Bang Nucleosynthesis" (http:/ / www. astro. ucla. edu/ ~wright/ BBNS. html). UCLA, Division of
Astronomy. . Retrieved 2007-02-22.
[12] Wallerstein, G; et al. (1999). "Synthesis of the elements in stars: forty years of progress" (http:/ / www. cococubed. com/ papers/
wallerstein97. pdf). Reviews of Modern Physics 69 (4): 9951084. Bibcode1997RvMP...69..995W. doi:10.1103/RevModPhys.69.995. .
[13] Earnshaw, A; Greenwood, N (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann.
[14] Croswell, K (1996). Alchemy of the Heavens (http:/ / kencroswell. com/ alchemy. html). Anchor. ISBN0-385-47214-5. .
[15] Ultratrace minerals. Authors: Nielsen, Forrest H. USDA, ARS Source: Modern nutrition in health and disease/editors, Maurice E. Shils ... et
al.. Baltimore : Williams & Wilkins, c1999., p. 283-303. Issue Date: 1999 URI: (http:/ / hdl. handle. net/ 10113/ 46493)
Chemical element
[16] Plato (2008) [c. 360 BC]. Timaeus (http:/ / books. google. com/ ?id=xSjvowNydN8C& lpg=PP1& dq=Plato timaeus&
pg=PA45#v=onepage& q=cube& f=false). Forgotten Books. p.45. ISBN978-1606200186. .
[17] Hillar, M (2004). "The Problem of the Soul in Aristotle's De anima" (http:/ / www. socinian. org/ aristotles_de_anima. html).
NASA/WMAP. . Retrieved 2006-08-10.
[18] Partington, JR (1937). A Short History of Chemistry. New York: Dover Publications. ISBN0486659771.
[19] Boyle, R (1661). The Sceptical Chymist. London. ISBN0922802904.
[20] Lavoisier, AL (1790). Elements of chemistry translated by Robert Kerr (http:/ / books. google. com/ ?id=4BzAjCpEK4gC& pg=PA175).
Edinburgh. pp.1756. ISBN9780415179140. .
[21] Transactinide-2 (http:/ / www. kernchemie. de/ Transactinides/ Transactinide-2/ transactinide-2. html). www.kernchemie.de
[22] Carey, GW (1914). The Chemistry of Human Life. Los Angeles. ISBN0766128407.
[23] Glanz, J (6 April 2010). "Scientists Discover Heavy New Element" (http:/ / www. nytimes. com/ 2010/ 04/ 07/ science/ 07element.
html?hp). New York Times. .
[24] Greiner, W. "Recommendations" (http:/ / www. jinr. ru/ img_sections/ PAC/ NP/ 31/ PAK_NP_31_recom_eng. pdf). 31st meeting, PAC for
Nuclear Physics. Joint Institute for Nuclear Research. .
[25] "IUPAC Announces Start of the Name Approval Process for the Element of Atomic Number 112" (http:/ / media. iupac. org/ news/
112_Naming_Process_20090720. pdf). IUPAC. 20 July 2009. . Retrieved 2009-08-27.
[26] "IUPAC (International Union of Pure and Applied Chemistry): Element 112 is Named Copernicium" (http:/ / www. iupac. org/ web/ nt/
2010-02-20_112_Copernicium). IUPAC. 20 February 2010. .
[27] Oganessian, YT; et al. (2006). "Synthesis of the isotopes of elements 118 and 116 in the 249Cf and 245Cm+48Ca fusion reactions". Physical
Review C 74: 044602. Bibcode2006PhRvC..74d4602O. doi:10.1103/PhysRevC.74.044602.
[28] "Two ultra-heavy elements added to the periodic table" (http:/ / www. wired. co. uk/ news/ archive/ 2011-06/ 06/ new-elements-added). 6
June 2011. .
Further reading
Ball, P (2004). The Elements: A Very Short Introduction. Oxford University Press. ISBN0192840991.
Emsley, J (2003). Nature's Building Blocks: An A-Z Guide to the Elements. Oxford University Press.
ISBN0198503407.
Gray, T (2009). The Elements: A Visual Exploration of Every Known Atom in the Universe. Black Dog &
Leventhal Publishers Inc. ISBN1579128149.
Scerri, ER (2007). The Periodic Table, Its Story and Its Significance. Oxford University Press.
Strathern, P (2000). Mendeleyev's Dream: The Quest for the Elements. Hamish Hamilton Ltd. ISBN024114065X.
External links
Videos for each element (http://periodicvideos.com/) by the University of Nottingham
148
Isotope
149
Isotope
Isotopes are variants of atoms of a particular chemical element, which have differing numbers of neutrons. Atoms of
a particular element by definition must contain the same number of protons but may have a distinct number of
neutrons which differs from atom to atom, without changing the designation of the atom as a particular element. The
number of nucleons (protons and neutrons) in the nucleus, known as the mass number, is not the same for two
isotopes of any element. For example, carbon-12, carbon-13 and carbon-14 are three isotopes of the element carbon
with mass numbers 12, 13 and 14 respectively. The atomic number of carbon is 6 (every carbon atom has 6 protons);
therefore the neutron numbers in these isotopes are 6, 7 and 8 respectively.
Ta (tantalum-180m).
Isotope
with half-lives longer than the age of the universe.
Adding in the radioactive nuclides that have been created artificially, there are more than 3100 currently known
nuclides.[2] These include 905 nuclides which are either stable, or have half-lives longer than 60 minutes. See list of
nuclides for details.
History
The existence of isotopes was first suggested in 1912 by the
radiochemist Frederick Soddy, based on studies of radioactive decay
chains which indicated about 40 different species between uranium and
lead. Since the periodic table only allowed for 11 elements from
uranium to lead, Soddy proposed that several types of atoms (differing
in radioactive properties) could occupy the same place in the table.[3]
The term isotope, Greek for at the same place, was suggested to
Soddy in 1914 by Margaret Todd, a Scottish physician to whom he was
distantly related by marriage, during a conversation in which he
explained his ideas to her.[4]
Confirmation was provided by the observation of isotopes differing in
mass for a stable (non-radioactive) element by J. J. Thomson in 1913.
As part of his exploration into the composition of canal rays (positive
ions), Thomson channeled streams of neon ions through a magnetic
and an electric field and measured their deflection by placing a
photographic plate in their path. Each stream created a glowing patch
In the bottom right corner of JJ Thomson's
on the plate at the point it struck. Thomson observed two separate
photographic plate are the separate impact marks
for the two isotopes of neon: neon-20 and
patches of light on the photographic plate (see image), which suggested
neon-22.
two different parabolas of deflection. Thomson eventually concluded
that some of the atoms in the neon gas were of higher mass than the
rest. F.W. Aston subsequently discovered different stable isotopes for numerous elements using a mass spectrograph.
150
Isotope
151
Isotope half-lives. Note that the plot for stable isotopes diverges from the line,
protons Z = neutrons N as the element number Z becomes larger
neutrons and protons; all heavier stable nuclides contain more neutrons than protons.
Isotope
152
154
Long-lived
25
All primordial
179
101 255
8
33
109 288
The proton:neutron ratio is not the only factor affecting nuclear stability. Adding neutrons to isotopes can vary their
nuclear spins and nuclear shapes, causing differences in neutron capture cross-sections and gamma spectroscopy and
nuclear magnetic resonance properties.
Even mass number
Even-mass-number nuclides, about = 154/255 = ~ 60% of all stable nuclides, are bosons, i.e. they have integer spin.
Almost all are even-proton, even-neutron (EE) nuclides, which necessarily have spin 0 because of pairing; only 5 are
odd-proton, odd-neutron nuclides, which have nonzero integer spin.
Pairing effects
Even/odd Z, N
p,n EE OO EO OE
Stable 148
54
48
21
56
53
Long-lived
Beta decay of an even-even nucleus produces an odd-odd nucleus, and vice versa. An even number of protons or of
neutrons are more stable (lower binding energy) because of pairing effects, so even-even nuclei are much more
stable than odd-odd. One effect is that there are few stable odd-odd nuclides, but another effect is to prevent beta
decay of many even-even nuclei into another even-even nucleus of the same mass number but lower energy, because
decay proceeding one step at a time would have to pass through an odd-odd nucleus of higher energy. Double beta
decay directly from even-even to even-even skipping over an odd-odd nuclide is only occasionally possible, and
even then with a half-life greater than a billion times the age of the universe. For example, the double beta emitter
116
Cd has a half-life of 2.91019 years. This makes for a larger number of stable even-even nuclides, up to three for
some mass numbers, and up to seven for some atomic (proton) numbers.
For example, the extreme stability of helium-4 due to a double pairing of 2 protons and 2 neutrons prevents any
nuclides containing five or eight nucleons from existing for long enough to serve as platforms for the buildup of
heavier elements via nuclear fusion in stars (see triple alpha process).
Isotope
153
K,
V,
La,
Li and
B are minority isotopes of elements that are rare compared to other light
elements, while the other six isotopes make up only a tiny percentage of their elements.
None of the primordial odd-odd nuclides have spin 0 in the ground state.
Odd mass number
For a given odd mass number, there can be only a single beta-stable nuclide, since there is not a difference in binding
energy between even-odd and odd-even comparable to that between even-even and odd-odd, leaving other nuclides
of the same mass number (isobars) free to beta decay towards the lowest-mass one. For 5, 147, 151, and 209+, the
beta-stable isobar of that mass number can alpha decay, giving a total of 101 stable nuclides with odd mass numbers.
Odd-mass-number nuclides are fermions, i.e. have half-integer spin. 29 of the 117 primordial odd-mass nuclides
have spin 1/2, 30 have spin 3/2, 24 have spin 5/2, 17 have spin 7/2, and 9 have spin 9/2.[7]
Odd proton-even neutron
These 48 stable nuclides form most of the stable isotopes of the odd-numbered elements; the few odd-odds are the
others. There are 41 odd-numbered elements with Z = 1 through 81, of which 32 have one stable odd-even isotope,
the elements technetium (43Tc) and promethium (61Pm) have no stable isotopes, and chlorine (17Cl), potassium
(19K), copper (29Cu), gallium (31Ga), bromine (35Br), silver (47Ag), antimony (51Sb), iridium (Ir|BL=77), and
thallium (81Tl), have two each, making a total of 48 stable odd-even isotopes. There are also five primordial
long-lived radioactive odd-even isotopes, Rb,
In,
Eu,
Re, and
Bi which was recently found to
decay.
Even proton-odd neutron
Isotope
154
Even-odd long-lived
Decay
Half-life
Cd
beta
7.71015 a
Sm
beta
1.061011 a
alpha
7.04108 a
odd number of neutrons. They are isotopes of even-Z elements, where they are a minority in comparison to the
even-even isotopes which are about 3 times as numerous. Only
isotopes in their element, the former only by a small margin, and the latter only because the expected beryllium-8 has
slightly lower binding energy than two alpha particles and therefore alpha decays.
Odd neutron number
Even Odd
Stable
197
58
Long-lived
24
67
Actinides with odd neutron number are generally fissile (with thermal neutrons), while those with even neutron
number are generally not, though they are fissionable with fast neutrons. Only
Pt, Be and N have odd
neutron number and are the most naturally abundant isotope of their element.
Occurrence in nature
Elements are composed of one or more naturally occurring isotopes. The unstable (radioactive) isotopes are either
primordial or postprimordial. Primordial isotopes were a product of stellar nucleosynthesis or another type of
nucleosynthesis such as cosmic ray spallation, and have persisted down to the present because their rate of decay is
so slow (e.g., uranium-238 and potassium-40). Postprimordial isotopes were created by cosmic ray bombardment as
cosmogenic nuclides (e.g., tritium, carbon-14), or by the decay of a radioactive primordial isotope to a radioactive
radiogenic nuclide daughter (e.g., uranium to radium). A few isotopes also continue to be naturally synthesized as
nucleogenic nuclides, by some other natural nuclear reaction, such as when neutrons from from natural nuclear
fission are absorbed by another atom.
As discussed above, only 80 elements have any stable isotopes, and 26 of these have only one stable isotope. Thus,
about two thirds of stable elements occur naturally on Earth in multiple stable isotopes, with the largest number of
stable isotopes for an element being ten, for tin (50Sn). There are about 94 elements found naturally on Earth (up to
plutonium inclusive), though some are detected only in very tiny amounts, such as plutonium-244. Scientists
estimate that the elements that occur naturally on Earth (some only as radioisotopes) occur as 339 isotopes (nuclides)
in total.[8] Only 255 of these naturally occurring isotopes are stable in the sense of never having been observed to
decay as of the present time An additional 33 primordial nuclides (to a total of 288 primordial nuclides), are
radioactive with known half-lives, but have half-lives longer than 80 million years, allowing them to exist from the
beginning of the solar system. See list of nuclides for details.
All the known stable isotopes occur naturally on Earth; the other naturally occurring-isotopes are radioactive but
occur on Earth due to their relatively long half-lives, or else due to other means of ongoing natural production. These
Isotope
include the afore-mentioned cosmogenic nuclides, the nucleogenic nuclides, and any radiogenic radioisotopes
formed by ongoing decay of a primordial radioactive isotope, such as radon and radium from uranium.
An additional ~3000 radioactive isotopes not found in nature have been created in nuclear reactors and in particle
accelerators. Many short-lived isotopes not found naturally on Earth have also been observed by spectroscopic
analysis, being naturally created in stars or supernovae. An example is aluminum-26, which is not naturally found on
Earth, but which is found in abundance on an astronomical scale.
The tabulated atomic masses of elements are averages that account for the presence of multiple isotopes with
different masses. Before the discovery of isotopes, empirically determined noninteger values of atomic mass
confounded scientists. For example, a sample of chlorine contains 75.8% chlorine-35 and 24.2% chlorine-37, giving
an average atomic mass of 35.5 atomic mass units.
According to generally accepted cosmology theory, only isotopes of hydrogen and helium, traces of some isotopes of
lithium and beryllium, and perhaps some boron, were created at the Big Bang, while all other isotopes were
synthesized later, in stars and supernovae, and in interactions between energetic particles such as cosmic rays, and
previously produced isotopes. (See nucleosynthesis for details of the various processes thought to be responsible for
isotope production.) The respective abundances of isotopes on Earth result from the quantities formed by these
processes, their spread through the galaxy, and the rates of decay for isotopes that are unstable. After the initial
coalescence of the solar system, isotopes were redistributed according to mass, and the isotopic composition of
elements varies slightly from planet to planet. This sometimes makes it possible to trace the origin of meteorites.
where m1, m2, ..., mN are the atomic masses of each individual isotope, and x1, ..., xN are the relative abundances of
these isotopes.
Applications of isotopes
Several applications exist that capitalize on properties of the various isotopes of a given element. Isotope separation
is a significant technological challenge, particularly with heavy elements such as uranium or plutonium. Lighter
elements such as lithium, carbon, nitrogen, and oxygen are commonly separated by gas diffusion of their compounds
such as CO and NO. The separation of hydrogen and deuterium is unusual since it is based on chemical rather than
physical properties, for example in the Girdler sulfide process. Uranium isotopes have been separated in bulk by gas
diffusion, gas centrifugation, laser ionization separation, and (in the Manhattan Project) by a type of production mass
spectrometry.
155
Isotope
Notes
Isotopes are nuclides having the same number of protons; compare:
Isotones are nuclides having the same number of neutrons.
Isobars are nuclides having the same mass number, i.e. sum of protons plus neutrons.
Nuclear isomers are different excited states of the same type of nucleus. A transition from one isomer to
another is accompanied by emission or absorption of a gamma ray, or the process of internal conversion. (Not
to be confused with chemical isomers.)
Bainbridge mass spectrometer
References
[1]
[2]
[3]
[4]
"Radioactives Missing From The Earth" (http:/ / www. don-lindsay-archive. org/ creation/ isotope_list. html). .
"NuDat 2 Description" (http:/ / www. nndc. bnl. gov/ nudat2/ help/ index. jsp). .
G.Choppin, J.O.Liljenzin and J.Rydberg Radiochemistry and Nuclear Chemistry (2d edn, Butterworth-Heinemann 1995), p.3-5
Budzikiewicz H and Grigsby RD (2006). "Mass spectrometry and isotopes: a century of research and discussion". Mass spectrometry reviews
25 (1): 14657. doi:10.1002/mas.20061. PMID16134128.
[5] Sonzogni, Alejandro (2008). "Interactive Chart of Nuclides" (http:/ / www. nndc. bnl. gov/ chart/ ). National Nuclear Data Center: Brook
haven National Laboratory. .
[6] http:/ / bryza. if. uj. edu. pl/ zdfk/ wp-includes/ publications/ misiaszek_180mTa_2009. pdf Search for the radioactivity of 180mTa using an
underground HPGe sandwich spectrometer, 2009
[7] http:/ / en. citizendium. org/ wiki/ Nuclear_magnetic_resonance/ Catalogs/ Magnetic_nuclei This reference also has 6 odd-odd nuclei, though
3 odd-odds are omitted. Antimony-123 and Tantalum-181 seem to have special-character typos that become apparent only on cut-paste and
automated search.
[8] http:/ / www. don-lindsay-archive. org/ creation/ isotope_list. html
156
Isotope
[9] E. Jamin et al. (2003). "Improved Detection of Added Water in Orange Juice by Simultaneous Determination of the Oxygen-18/Oxygen-16
Isotope Ratios of Water and Ethanol Derived from Sugars" (http:/ / pubs. acs. org/ cgi-bin/ article. cgi/ jafcau/ 2003/ 51/ i18/ pdf/ jf030167&
nbsp;m. pdf). J. Agric. Food Chem. 51: 5202. doi:10.1021/jf030167m. .
[10] A. H. Treiman, J. D. Gleason and D. D. Bogard (2000). "The SNC meteorites are from Mars" (http:/ / www. sciencedirect. com/
science?_ob=ArticleURL& _udi=B6V6T-41WBDHD-8& _user=2400262& _coverDate=10/ 31/ 2000& _alid=678948366& _rdoc=3&
_fmt=summary& _orig=search& _cdi=5823& _sort=r& _docanchor=& view=c& _ct=89& _acct=C000057185& _version=1&
_urlVersion=0& _userid=2400262& md5=c5ae2aa8ea60dbd76c2870048730a299). Planet. Space. Sci. 48 (1214): 1213.
Bibcode2000P&SS...48.1213T. doi:10.1016/S0032-0633(00)00105-7. .
External links
National Nuclear Data Center (http://www.nndc.bnl.gov/) Portal to large repository of free data and analysis
programs from NNDC
National Isotope Development Center (http://isotopes.gov/) Coordination and management of the production,
availability, and distribution of isotopes, and reference information for the isotope community
Isotope Development & Production for Research and Applications (IDPRA) (http://science.energy.gov/np/
research/idpra/) U.S. Department of Energy program for isotope production and production research and
development
Nucleonica Nuclear Science Portal (http://www.nucleonica.net) (free, registration required)
Nucleonica Nuclear Science Wiki (http://www.nucleonica.net/wiki/index.php/Special:Allpages/Help:)
International Atomic Energy Agency (http://www.IAEA.org) Homepage of International Atomic Energy
Agency (IAEA), an Agency of the United Nations (UN)
Atomic Weights and Isotopic Compositions for All Elements (http://physics.nist.gov/cgi-bin/Compositions/
stand_alone.pl?ele=&ascii=html&isotype=some) Static table, from NIST (National Institute of Standards and
Technology)
Atomgewichte, Zerfallsenergien und Halbwertszeiten aller Isotope (http://atom.kaeri.re.kr/)
Chart of the Nuclides (http://www.nuclidechart.com/) produced by the Knolls Atomic Power Laboratory $25
Exploring the Table of the Isotopes (http://ie.lbl.gov/education/isotopes.htm) at the LBNL
Current isotope research and information (http://www.isotope.info/) isotope.info
Emergency Preparedness and Response: Radioactive Isotopes (http://www.bt.cdc.gov/radiation/isotopes/) by
the CDC (Centers for Disease Control and Prevention)
Chart of Nuclides (http://www.nndc.bnl.gov/chart/) Interactive Chart of Nuclides (National Nuclear Data
Center)
Interactive Chart of the nuclides, isotopes and Periodic Table (http://www.yoix.org/elements.html)
157
Ion
158
Ion
An ion is an atom or molecule in which
the total number of electrons is not equal
to the total number of protons, giving it a
net positive or negative electrical charge.
The name was given by physicist
Michael Faraday for the substances that
allow a current to pass ("go") between
electrodes in a solution, when an electric
field is applied. It is from Greek ,
meaning "going".
An ion consisting of a single atom is an
atomic or monatomic ion; if it consists
of two or more atoms, it is a molecular
or polyatomic ion.
Hydrogen atom (center) contains a single proton and a single electron. Removal of the
electron gives a cation (left), whereas addition of an electron gives an anion (right).
The hydrogen anion, with its loosely held two-electron cloud, has a larger radius than
the neutral atom, which in turn is much larger than the bare proton of the cation.
Hydrogen forms the only cation that has no electrons, but even cations that (unlike
hydrogen) still retain one or more electrons, are still smaller than the neutral atoms or
molecules from which they are derived.
General
History and discovery
Etymologically the word ion is the Greek (going), the present participle of , ienai, "to go". This term was
introduced by English physicist and chemist Michael Faraday in 1834 for the (then unknown) species that goes from
one electrode to the other through an aqueous medium.[1] [2] Faraday did not know the nature of these species, but he
knew that since metals dissolved into and entered solution at one electrode, and new metal came forth from solution
at the other electrode, that some kind of substance moved through the solution in a current, conveying matter from
one place to the other.
Faraday also introduced the words anion for a negatively charged ion, and cation for a positively charged one. In
Faraday's nomenclature, cations were named because they were attracted to the cathode in a galvanic device and
anions were named due to their attraction to the anode.
Ion
159
Characteristics
Ions in their gas-like state are highly reactive, and do not occur in large amounts on Earth, except in flames,
lightning, electrical sparks, and other plasmas. These gas-like ions rapidly interact with ions of opposite charge to
give neutral molecules or ionic salts. Ions are also produced in the liquid or solid state when salts interact with
solvents (for example, water) to produce "solvated ions," which are more stable, for reasons involving a combination
of energy and entropy changes as the ions move away from each other to interact with the liquid. These stabilized
species are more commonly found in the environment at low temperatures. A common example is the ions present in
seawater, which are derived from the dissolved salts there.
All ions are charged, which means that like all charged objects they are attracted to opposite electric charges (positive to negative, and vice versa),
repelled by like charges, and
when moving, travel in trajectories that are deflected by a magnetic field.
Electrons, due to their smaller mass and thus larger space-filling properties as matter waves, determine the size of
atoms and molecules that possess any electrons at all. Thus, anions (negatively charged ions) are larger than the
parent molecule or atom, as the excess electron(s) repel each other, and add to the physical size of the ion, because
its size is determined by its electron cloud. Conversely, cations are generally smaller than the corresponding parent
atom or molecule, for the same reason. One particular cation (that of hydrogen) contains no electrons, and thus is
very much smaller than the parent hydrogen atom.
Natural occurrences
Ions are ubiquitous in nature and are responsible for diverse phenomena from the luminescence of the Sun, to the
existence of the Earth's ionosphere. Atoms in their ionic state may have a different color from neutral atoms, and
thus light absorption by metal ions gives the color of gemstones. In both inorganic and organic chemistry (including
biochemistry), the interaction of water and ions is extremely important; an example is the energy that drives
breakdown of ATP. The following sections describe contexts in which ions feature prominently, these are arranged
in decreasing physical length-scale, from the astronomical to the microscopic.
Astronomical
A collection of non-aqueous gas-like ions, or even a gas
containing a proportion of charged particles, is called a plasma.
>99.9% of visible matter in the Universe may be in the form of
plasmas.[3] These include our Sun and other stars, the space
between planets, as well as the space in between stars. Plasmas are
often called the fourth state of matter because its properties are
substantially different from solids, liquids, and gases.
Astrophysical plasmas predominantly contain a mixture of
electrons and protons (ionized hydrogen).
Related technology
Ions can be non-chemically prepared using various ion sources,
usually involving high voltage or temperature. These are used in a
multitude of devices such as mass spectrometers, optical emission
spectrometers, particle accelerators, ion implanters and ion
engines.
Ion
160
As reactive charged particles, they are also used in air purification by disrupting microbes, and in household items
such as smoke detectors.
As signaling and metabolism in organisms are controlled by a precise ionic gradient across membranes, the
disruption of this gradient contributes to cell death. This is a common mechanism exploited by natural and artificial
biocides, including the ion channels gramicidin and amphotericin (a fungicide).
Inorganic dissolved ions are a component of total dissolved solids, an indicator of water quality in the world.
Chemistry
Notation
Denoting the charged state
When writing the chemical formula for an ion, its net charge is written
in superscript immediately after the chemical structure for the
molecule/atom. The net charge is written with the magnitude before the
sign; that is, a doubly charged cation is indicated as 2+ instead of +2.
Conventionally the magnitude of the charge is omitted for singly
charged molecules/atoms; for example, the sodium cation is indicated
as Na+ and not Na1+.
An alternative (and acceptable) way of showing a molecule/atom with multiple charges is by drawing out the signs
multiple times; this is often seen with transition metals. Chemists sometimes circle the sign; this is merely
ornamental and does not alter the chemical meaning. All three representations of Fe2+ shown in the figure are thus
equivalent.
Monatomic ions are sometimes also denoted with Roman numerals; for
example, the Fe2+ example seen above is occasionally referred to as
Fe(II) or FeII. The Roman numeral designates the formal oxidation
state of an element, whereas the superscripted numerals denotes the net
charge. The two notations are therefore exchangeable for monatomic
ions, but the Roman numerals cannot be applied to polyatomic ions. It
is however possible to mix the notations for the individual metal center
with a polyatomic complex, as shown by the uranyl ion example.
Sub-classes
Ion
161
Formation
Formation of monatomic ions
Monatomic ions are formed by the addition of electrons to the valence shell of the atom, which is the outer-most
electron shell in an atom, or the losing of electrons from this shell. The inner shells of an atom are filled with
electrons that are tightly bound to the positively charged atomic nucleus, and so do not participate in this kind of
chemical interaction. The process of gaining or losing electrons from a neutral atom or molecule is called ionization.
Atoms can be ionized by bombardment with radiation, but the more usual process of ionization encountered in
chemistry is the transfer of electrons between atoms or molecules. This transfer is usually driven by the attaining of
stable ("closed shell") electronic configurations. Atoms will gain or lose electrons depending on which action takes
the least energy.
For example, a sodium atom, Na, has a single electron in its valence shell, surrounding 2 stable, filled inner shells of
2 and 8 electrons. Since these filled shells are very stable, a sodium atom tends to lose its extra electron and attain
this stable configuration, becoming a sodium cation in the process
Na Na+ + e
On the other hand, a chlorine atom, Cl, has 7 electrons in its valence shell, which is one short of the stable, filled
shell with 8 electrons. Thus, a chlorine atom tends to gain an extra electron and attain a stable 8-electron
configuration, becoming a chloride anion in the process:
Cl + e Cl
This driving force is what causes sodium and chlorine to undergo a chemical reaction, where the "extra" electron is
transferred from sodium to chlorine, forming sodium cations and chloride anions. Being oppositely charged, these
cations and anions form ionic bonds and combine together to form sodium chloride, NaCl, more commonly known
as rock salt.
Na+ + Cl NaCl
Formation of polyatomic and molecular ions
Polyatomic and molecular ions are often formed by the gaining or
losing of elemental ions such as H+ in neutral molecules. For
example, when ammonia, NH3, accepts a proton, H+, it forms the
ammonium ion, NH . Ammonia and ammonium have the same
number of electrons in essentially the same electronic
configuration, but ammonium has an extra proton that gives it a
net positive charge.
Ammonia can also lose an electron to gain a positive charge,
forming the ion NH . However, this ion is unstable, because it
has an incomplete valence shell around the nitrogen atom, making
it a very reactive radical ion.
Due to the instability of radical ions, polyatomic and molecular
ions are usually formed by gaining or losing elemental ions such
as H+, rather than gaining or losing electrons. This allows the
molecule to preserve its stable electronic configuration while
acquiring an electrical charge.
Ionization potential
Ion
162
The energy required to detach an electron in its lowest energy state from an atom or molecule of a gas with less net
electric charge is called the ionization potential, or ionization energy. The nth ionization energy of an atom is the
energy required to detach its nth electron after the first n 1 electrons have already been detached.
Each successive ionization energy is markedly greater than the last. Particularly great increases occur after any given
block of atomic orbitals is exhausted of electrons. For this reason, ions tend to form in ways that leave them with full
orbital blocks. For example, sodium has one valence electron in its outermost shell, so in ionized form it is
commonly found with one lost electron, as Na+. On the other side of the periodic table, chlorine has seven valence
electrons, so in ionized form it is commonly found with one gained electron, as Cl. Caesium has the lowest
measured ionization energy of all the elements and helium has the greatest.[4] The ionization energy of metals is
generally much lower than the ionization energy of nonmetals, which is why metals will generally lose electrons to
form positively charged ions while nonmetals will generally gain electrons to form negatively charged ions.
Ionic bonding
Ionic bonding is a kind of chemical bonding that arises from the mutual attraction of oppositely charged ions. Since
ions of like charge repel each other, they do not usually exist on their own. Instead, many of them may form a crystal
lattice, in which ions of opposite charge are bound to each other. The resulting compound is called an ionic
compound, and is said to be held together by ionic bonding. In ionic compounds there arise characteristic distances
between ion neighbors from which the spatial extension and the ionic radius of individual ions may be derived.
The most common type of ionic bonding is seen in compounds of metals and nonmetals (except noble gases, which
rarely form chemical compounds). Metals are characterized by having a small number of electrons in excess of a
stable, closed-shell electronic configuration. As such, they have the tendency to lose these extra electrons in order to
attain a stable configuration. This property is known as electropositivity. Non-metals, on the other hand, are
characterized by having an electron configuration just a few electrons short of a stable configuration. As such, they
have the tendency to gain more electrons in order to achieve a stable configuration. This tendency is known as
electronegativity. When a highly electropositive metal is combined with a highly electronegative nonmetal, the extra
electrons from the metal atoms are transferred to the electron-deficient nonmetal atoms. This reaction produces metal
cations and nonmetal anions, which are attracted to each other to form a salt.
Chemical applications
Gas-like ions and solvated ions both have tremendous impact on chemical analysis and synthesis.
Catalysis
Common ions
Common Cations
Common Name
Formula
Historic Name
Simple Cations
Aluminium
Al3+
Calcium
Ca2+
Copper(II)
Cu2+
Hydrogen
H+
Iron(II)
Fe2+
cupric
ferrous
Ion
163
Iron(III)
Fe3+
ferric
Magnesium
Mg2+
Mercury(II)
Hg2+
mercuric
Potassium
K+
kalic
Silver
Ag+
Sodium
Na+
natric
Polyatomic Cations
Ammonium
NH
Oxonium
H3O+
hydronium
Mercury(I)
Hg
mercurous
Common Anions
Formal Name
Formula
Alt. Name
Simple Anions
Chloride
Cl
Fluoride
Bromide
Br
Oxide
O2
Oxoanions
Carbonate
CO
OH
Nitrate
NO
Phosphate
PO
Sulfate
SO
bicarbonate
CH3COO ethanoate
Formate
HCOO
methanoate
Oxalate
C2O
ethandioate
Cyanide
CN
Ion
164
References
[1] BBC - Michael Faraday (http:/ / www. bbc. co. uk/ history/ historic_figures/ faraday_michael. shtml). UK: BBC. .
[2] "Online etymology dictionary" (http:/ / www. etymonline. com/ index. php?term=ion). . Retrieved 2011-01-07.
[3] Plasma, Plasma, Everywhere (http:/ / science. nasa. gov/ newhome/ headlines/ ast07sep99_1. htm) Science@NASA Headline news, Space
Science n 158, September 7, 1999.
[4] Chemical elements listed by ionization energy (http:/ / www. lenntech. com/ Periodic-chart-elements/ ionization-energy. htm)
Molecule
A molecule (pronounced/mlkjul/) is
an electrically neutral group of at least
two atoms held together by covalent
chemical bonds.[1] [2] [3] [4] [5] [6]
Molecules are distinguished from ions
by their electrical charge. However, in
quantum physics, organic chemistry,
3D (left and center) and 2D (right) representations of the terpenoid molecule atisane
and biochemistry, the term molecule is
often used less strictly and applied to polyatomic ions.
In the kinetic theory of gases, the term molecule is often used for any gaseous particle regardless of its composition.
According to this definition noble gas atoms are considered molecules despite the fact that they are composed of a
single non-bonded atom.[7]
A molecule may consist of atoms of a single chemical element, as with oxygen (O2), or of different elements, as with
water (H2O). Atoms and complexes connected by non-covalent bonds such as hydrogen bonds or ionic bonds are
generally not considered single molecules.[8]
Molecules as components of matter are common in organic substances (and therefore biochemistry). They also make
up most of the oceans and atmosphere. However, the majority of familiar solid substances on Earth, including most
of the minerals that make up the crust, mantle, and core of the Earth, contain many chemical bonds, but are not made
of identifiable molecules. Also, no typical molecule can be defined for ionic crystals (salts) and covalent crystals
(network solids), although these are often composed of repeating unit cells that extend either in a plane (such as in
graphene) or three-dimensionally (such as in diamond, quartz, or sodium chloride). The theme of repeated
unit-cellular-structure also holds for most condensed phases with metallic bonding, which means that solid metals
are also not made of molecules. In glasses (solids that exist in a vitreous disordered state), atoms may also be held
together by chemical bonds without presense of any definable molecule, but also without any of the regularity of
repeating units that characterises crystals.
Molecular science
The science of molecules is called molecular chemistry or molecular physics, depending on the focus. Molecular
chemistry deals with the laws governing the interaction between molecules that results in the formation and breakage
of chemical bonds, while molecular physics deals with the laws governing their structure and properties. In practice,
however, this distinction is vague. In molecular sciences, a molecule consists of a stable system (bound state)
comprising two or more atoms. Polyatomic ions may sometimes be usefully thought of as electrically charged
molecules. The term unstable molecule is used for very reactive species, i.e., short-lived assemblies (resonances) of
electrons and nuclei, such as radicals, molecular ions, Rydberg molecules, transition states, van der Waals
complexes, or systems of colliding atoms as in Bose-Einstein condensate
Molecule
165
Molecular size
Most molecules are far too small to be seen with the naked eye, but there are exceptions. DNA, a macromolecule,
can reach macroscopic sizes, as can molecules of many polymers. The smallest molecule is the diatomic hydrogen
(H2), with a bond length of 0.74 .[10] Molecules commonly used as building blocks for organic synthesis have a
dimension of a few to several dozen . Single molecules cannot usually be observed by light (as noted above), but
small molecules and even the outlines of individual atoms may be traced in some circumstances by use of an atomic
force microscope. Some of the largest molecules are macromolecules or supermolecules.
Radius
Effective molecular radius is the size a molecule displays in solution.[11]
different substances contains examples.
[12]
Molecular formula
A compound's empirical formula is the simplest integer ratio of the chemical elements that constitute it. For example,
water is always composed of a 2:1 ratio of hydrogen to oxygen atoms, and ethyl alcohol or ethanol is always
composed of carbon, hydrogen, and oxygen in a 2:6:1 ratio. However, this does not determine the kind of molecule
uniquely dimethyl ether has the same ratios as ethanol, for instance. Molecules with the same atoms in different
arrangements are called isomers. Also carbohydrates, for example, have the same ratio (carbon:hydrogen:oxygen =
1:2:1) (and thus the same empirical formula) but different total numbers of atoms in the molecule.
The molecular formula reflects the exact number of atoms that compose the molecule and so characterizes different
molecules. However different isomers can have the same atomic composition while being different molecules.
The empirical formula is often the same as the molecular formula but not always. For example, the molecule
acetylene has molecular formula C2H2, but the simplest integer ratio of elements is CH.
The molecular mass can be calculated from the chemical formula and is expressed in conventional atomic mass units
equal to 1/12 of the mass of a neutral carbon-12 (12C isotope) atom. For network solids, the term formula unit is used
in stoichiometric calculations.
Molecule
Molecular geometry
Molecules have fixed equilibrium geometriesbond lengths and angles about which they continuously oscillate
through vibrational and rotational motions. A pure substance is composed of molecules with the same average
geometrical structure. The chemical formula and the structure of a molecule are the two important factors that
determine its properties, particularly its reactivity. Isomers share a chemical formula but normally have very
different properties because of their different structures. Stereoisomers, a particular type of isomers, may have very
similar physico-chemical properties and at the same time different biochemical activities.
Molecular spectroscopy
Molecular spectroscopy deals with the response (spectrum) of molecules interacting with probing signals of known
energy (or frequency, according to Planck's formula). Molecules have quantized energy levels that can be analyzed
by detecting the molecule's energy exchange through absorbance or emission.[13] Spectroscopy does not generally
refer to diffraction studies where particles such as neutrons, electrons, or high energy X-rays interact with a regular
arrangement of molecules (as in a crystal).
Theoretical aspects
The study of molecules by molecular physics and theoretical chemistry is largely based on quantum mechanics and
is essential for the understanding of the chemical bond. The simplest of molecules is the hydrogen molecule-ion,
H2+, and the simplest of all the chemical bonds is the one-electron bond. H2+ is composed of two positively charged
protons and one negatively charged electron, which means that the Schrdinger equation for the system can be
solved more easily due to the lack of electronelectron repulsion. With the development of fast digital computers,
approximate solutions for more complicated molecules became possible and are one of the main aspects of
computational chemistry.
When trying to define rigorously whether an arrangement of atoms is "sufficiently stable" to be considered a
molecule, IUPAC suggests that it "must correspond to a depression on the potential energy surface that is deep
enough to confine at least one vibrational state".[1] This definition does not depend on the nature of the interaction
between the atoms, but only on the strength of the interaction. In fact, it includes weakly bound species that would
not traditionally be considered molecules, such as the helium dimer, He2, which has one vibrational bound state[14]
and is so loosely bound that it is only likely to be observed at very low temperatures.
References
[1] IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (1994) " molecule (http:/ /
goldbook. iupac. org/ M04002. html)".
[2] Pauling, Linus (1970). General Chemistry. New York: Dover Publications, Inc.. ISBN0-486-65622-5.
[3] Ebbin, Darrell, D. (1990). General Chemistry, 3rd Ed.. Boston: Houghton Mifflin Co.. ISBN0-395-43302-9.
[4] Brown, T.L. (2003). Chemistry the Central Science, 9th Ed.. New Jersey: Prentice Hall. ISBN0-13-066997-0.
[5] Chang, Raymond (1998). Chemistry, 6th Ed.. New York: McGraw Hill. ISBN0-07-115221-0.
[6] Zumdahl, Steven S. (1997). Chemistry, 4th ed.. Boston: Houghton Mifflin. ISBN0-669-41794-7.
[7] Chandra, Sulekh. Comprehensive Inorganic Chemistry. New Age Publishers. ISBN8122415121.
[8] Molecule (http:/ / www. britannica. com/ EBchecked/ topic/ 388236/ molecule), Encyclopaedia Britannica on-line
[9] Molecule Definition (http:/ / antoine. frostburg. edu/ chem/ senese/ 101/ glossary/ m. shtml#molecule) (Frostburg State University)
[10] Roger L. DeKock, Harry B. Gray (1989). Chemical structure and bonding (http:/ / books. google. com/ ?id=q77rPHP5fWMC& pg=PA199).
University Science Books. p.199. ISBN093570261X. .
[11] Chang RL, Deen WM, Robertson CR, Brenner BM. (1975). "Permselectivity of the glomerular capillary wall: III. Restricted transport of
polyanions". Kidney Int. 8 (4): 212218. doi:10.1038/ki.1975.104. PMID1202253.
[12] Chang RL, Ueki IF, Troy JL, Deen WM, Robertson CR, Brenner BM. (1975). "Permselectivity of the glomerular capillary wall to
macromolecules. II. Experimental studies in rats using neutral dextran". Biophys J. 15 (9): 887906. Bibcode1975BpJ....15..887C.
doi:10.1016/S0006-3495(75)85863-2. PMC1334749. PMID1182263.
166
Molecule
[13] IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (1997,2006) " spectroscopy
(http:/ / goldbook. iupac. org/ {{{file}}}. html)".
[14] Anderson JB (May 2004). "Comment on "An exact quantum Monte Carlo calculation of the helium-helium intermolecular potential" [J.
Chem. Phys. 115, 4546 (2001)]". J Chem Phys 120 (20): 98867. Bibcode2004JChPh.120.9886A. doi:10.1063/1.1704638. PMID15268005.
External links
Molecule of the Month (http://www.chm.bris.ac.uk/motm/motm.htm) School of Chemistry, University of
Bristol
Chemical compound
A chemical compound is a pure chemical substance consisting of two or more different chemical elements[1] [2] [3]
that can be separated into simpler substances by chemical reactions.[4] Chemical compounds have a unique and
defined chemical structure; they consist of a fixed ratio of atoms[3] that are held together in a defined spatial
arrangement by chemical bonds. Chemical compounds can be molecular compounds held together by covalent
bonds, salts held together by ionic bonds, intermetallic compounds held together by metallic bonds, or complexes
held together by coordinate covalent bonds. Pure chemical elements are not considered chemical compounds, even if
they consist of molecules which contain only multiple atoms of a single element (such as H2, S8, etc.),[5] which are
called diatomic molecules or polyatomic molecules.
Wider definitions
There are exceptions to the definition above, and large amounts of the solid chemical matter familiar on Earth do not
have simple formulas. Certain crystalline compounds are called "non-stoichiometric" because they vary in
composition due to either the presence of foreign elements trapped within the crystal structure or a deficit or excess
of the constituent elements. Such non-stoichiometric compounds form most of the crust and mantle of the Earth.
Other compounds regarded as chemically identical may have varying amounts of heavy or light isotopes of the
constituent elements, which will make the ratio of elements by mass vary slightly.
Elementary concepts
Characteristic properties of compounds:
1. Elements in a compound are present in a definite proportion
Example- 2 atoms of hydrogen + 1 atom of oxygen becomes 1 molecule of compound-water.
2. Compounds have a definite set of properties
Elements comprising a compound do not retain their original properties.
Example: hydrogen (element, which is combustible and non-supporter of combustion) + oxygen (element, which is
non-combustible and supporter of combustion) becomes water (compound, which is non-combustible and
non-supporter of combustion)
Valency is the number of hydrogen atoms which can combine with one atom of the element forming a compound.
167
Chemical compound
Formula
Chemists describe compounds using formulas in various formats. For compounds that exist as molecules, the
formula for the molecular unit is shown. For polymeric materials, such as minerals and many metal oxides, the
empirical formula is normally given, e.g. NaCl for table salt.
The elements in a chemical formula are normally listed in a specific order, called the Hill system. In this system, the
carbon atoms (if there are any) are usually listed first, any hydrogen atoms are listed next, and all other elements
follow in alphabetical order. If the formula contains no carbon, then all of the elements, including hydrogen, are
listed alphabetically. There are, however, several important exceptions to the normal rules. For ionic compounds, the
positive ion is almost always listed first and the negative ion is listed second. For oxides, oxygen is usually listed
last.
Organic acids generally follow the normal rules with C and H coming first in the formula. For example, the formula
for trifluoroacetic acid is usually written as C2HF3O2. More descriptive formulas can convey structural information,
such as writing the formula for trifluoroacetic acid as CF3CO2H. On the other hand, the chemical formulas for most
inorganic acids and bases are exceptions to the normal rules. They are written according to the rules for ionic
compounds (positive first, negative second), but they also follow rules that emphasize their Arrhenius definitions.
Specifically, the formula for most inorganic acids begins with hydrogen and the formula for most bases ends with the
hydroxide ion (OH-). Formulas for inorganic compounds do not often convey structural information, as illustrated by
the common use of the formula H2SO4 for a molecule (sulfuric acid) that contains no H-S bonds. A more descriptive
presentation would be O2S(OH)2, but it is almost never written this way.
168
Chemical compound
CAS number
Every chemical substance, including chemical compounds, that has been described in the literature carries a unique
numerical identifier, its CAS number.
References
[1] Brown, Theodore L.; LeMay, H. Eugene; Bursten, Bruce E.; Murphy, Catherine J.; Woodward, Patrick (2009), Chemistry: The Central
Science, AP Edition (http:/ / www. pearsonschool. com/ index. cfm?locator=PSZ16f& PMDBSUBCATEGORYID=& PMDBSITEID=2781&
PMDBSUBSOLUTIONID=& PMDBSOLUTIONID=6724& PMDBSUBJECTAREAID=& PMDBCATEGORYID=814&
PMDbProgramId=52962) (11th ed.), Upper Saddle River, NJ: Pearson/Prentice Hall, pp.56, ISBN0132364891,
[2] Hill, John W.; Petrucci, Ralph H.; McCreary, Terry W.; Perry, Scott S. (2005), General Chemistry (http:/ / www. pearsonhighered. com/
educator/ academic/ product/ 0,3110,0131402838,00. html) (4th ed.), Upper Saddle River, NJ: Pearson/Prentice Hall, p.6,
ISBN9780131402836,
[3] Whitten, Kenneth W.; Davis, Raymond E.; Peck, M. Larry (2000), General Chemistry (6th ed.), Fort Worth, TX: Saunders College
Publishing/Harcourt College Publishers, p.15, ISBN9780030723735
[4] Wilbraham, Antony; Matta, Michael; Staley, Dennis; Waterman, Edward (2002), Chemistry (1st ed.), Upper Saddle River, NJ:
Pearson/Prentice Hall, p.36, ISBN0132512106
[5] Halal, John (2008), "Chapter 8: General Chemistry" (http:/ / www. wadsworthmedia. com/ marketing/ sample_chapters/ 156253629X_ch08.
pdf), Milady's Hair Structure and Chemistry Simplified (5 ed.), Milady Publishing, pp.9698, ISBN1428335587,
Further reading
Robert Siegfried (2002). From elements to atoms: a history of chemical composition. American Philosophical
Society. ISBN978-0-87169-924-4.
169
Chemical substance
170
Chemical substance
In chemistry, a chemical substance is a form of matter that has
constant chemical composition and characteristic properties.[1] It
cannot be separated into components by physical separation methods,
i.e. without breaking chemical bonds. They can be solids, liquids or
gases.
Chemical substances are often called 'pure' to set them apart from
mixtures. A common example of a chemical substance is pure water; it
has the same properties and the same ratio of hydrogen to oxygen
whether it is isolated from a river or made in a laboratory. Other
chemical substances commonly encountered in pure form are diamond
(carbon), gold, table salt (sodium chloride) and refined sugar (sucrose).
However, simple or seemingly pure substances found in nature can in
fact be mixtures of chemical substances. For example, tap water may
contain small amounts of dissolved sodium chloride and compounds
containing iron, calcium and many other chemical substances.
Definition
Chemical substances (also called pure substances) are often defined as
"any material with a definite chemical composition" in most
introductory general chemistry textbooks.[2] According to this
definition a chemical substance can either be a pure chemical element
or a pure chemical compound. But, there are exceptions to this
definition; a pure substance can also be defined as a form of matter that
has both definite composition and distinct properties.[3] The chemical
substance index published by CAS also includes several alloys of
uncertain composition.[4] Non-stoichiometric compounds are a special
A colorful group of chemicals
case (in inorganic chemistry) that violates the law of constant
composition, and for them, it is sometimes difficult to draw the line
between a mixture and a compound, as in the case of palladium hydride. Broader definitions of chemicals or
chemical substances can be found, for example: "the term 'chemical substance' means any organic or inorganic
substance of a particular molecular identity, including (i) any combination of such substances occurring in whole
or in part as a result of a chemical reaction or occurring in nature"[5]
Chemical substance
History
The concept of a "chemical substance" became firmly established in the late eighteenth century after work by the
chemist Joseph Proust on the composition of some pure chemical compounds such as basic copper carbonate.[6] He
deduced that, "All samples of a compound have the same composition; that is, all samples have the same
proportions, by mass, of the elements present in the compound." This is now known as the law of constant
composition.[7] Later with the advancement of methods for chemical synthesis particularly in the realm of organic
chemistry; the discovery of many more chemical elements and new techniques in the realm of analytical chemistry
used for isolation and purification of elements and compounds from chemicals that led to the establishment of
modern chemistry, the concept was defined as is found in most chemistry textbooks. However, there are some
controversies regarding this definition mainly because the large number of chemical substances reported in
chemistry literature need to be indexed.
Chemical elements
An element is a chemical substance that is made up of a particular kind of atoms and hence cannot be broken down
or transformed by a chemical reaction into a different element, though it can be transmutated into another element
through a nuclear reaction. This is so, because all of the atoms in a sample of an element have the same number of
protons, though they may be different isotopes, with differing numbers of neutrons.
There are about 120 known elements, about 80 of which are stable that is, they do not change by radioactive decay
into other elements. However, the number of chemical substances that are elements can be more than 120, because
some elements can occur as more than a single chemical substance (allotropes). For instance, oxygen exists as both
diatomic oxygen (O2) and ozone (O3). The majority of elements are classified as metals. These are elements with a
characteristic lustre such as iron, copper, and gold. Metals typically conduct electricity and heat well, and they are
malleable and ductile.[8] Around a dozen elements,[9] such as carbon, nitrogen, and oxygen, are classified as
non-metals. Non-metals lack the metallic properties described above, they also have a high electronegativity and a
tendency to form negative ions. Certain elements such as silicon sometimes resemble metals and sometimes
resemble non-metals, and are known as metalloids.
Chemical compounds
A pure chemical compound is a chemical substance that is composed of a particular set of molecules or ions. Two or
more elements combined into one substance through a chemical reaction form a chemical compound. All compounds
are substances, but not all substances are compounds.
A chemical compound can be either atoms bonded together in molecules or crystals in which atoms, molecules or
ions form a crystalline lattice. Compounds based primarily on carbon and hydrogen atoms are called organic
compounds, and all others are called inorganic compounds. Compounds containing bonds between carbon and a
metal are called organometallic compounds.
Compounds in which components share electrons are known as covalent compounds. Compounds consisting of
oppositely charged ions are known as ionic compounds, or salts.
In organic chemistry, there can be more than one chemical compound with the same composition and molecular
weight. Generally, these are called isomers. Isomers usually have substantially different chemical properties, may be
isolated and do not spontaneously convert to each other. A common example is glucose vs. fructose. The former is
an aldehyde, the latter is a ketone. Their interconversion requires either enzymatic or acid-base catalysis. However,
there are also tautomers, where isomerization occurs spontaneously, such that a pure substance cannot be isolated
into its tautomers. A common example is glucose, which has open-chain and ring forms. One cannot manufacture
pure open-chain glucose because glucose spontaneously cyclizes to the hemiacetal form.
171
Chemical substance
172
Chemical substance
173
alcohol, or
ethyl alcohol
ethanol
C2H5OH
Chemical structure
InChI
1/C2H6O/c1-2-3/h3H,2H2,1H3
Chemical substance
[8] Hill, J. W.; Petrucci, R. H.; McCreary, T. W.; Perry, S. S. General Chemistry, 4th ed., pp4546, Pearson Prentice Hall, Upper Saddle River,
New Jersey, 2005.
[9] The boundary between metalloids and non-metals is imprecise, as explained in the previous reference.
[10] What is a chemical (http:/ / www. nicnas. gov. au/ Industry/ New_Chemicals/ Does_My_Chemical_Require_Notification/
What_Is_A_Chemical. asp)
[11] BfR Chemicals (http:/ / www. bfr. bund. de/ cd/ 569)
[12] There is only one definition for "chemical", that of a substance, in the US Unabridged Edition of the Random House Dictionary of the
English Language, New York, 1966.
[13] Coping with the Growth of Chemical Knowledge: Challenges for Chemistry Documentation, Education, and Working Chemists (http:/ /
www. rz. uni-karlsruhe. de/ ~ed01/ Jslit/ eduquim. htm)
[14] Chemical Abstracts substance count (http:/ / www. cas. org/ newsevents/ releases/ 60millionth052011. html)
174
175
Phases
176
Types of phases
Distinct phases may be described as
different states of matter such as gas,
liquid, solid, plasma or BoseEinstein
condensate.
Useful
mesophases
between solid and liquid form other
states of matter.
Distinct phases may also exist within a
given state of matter. As shown in the
diagram for iron alloys, several phases
exist for both the solid and liquid
states.
Phases
may
also
be
differentiated based on solubility as in
polar (hydrophilic) or non-polar
(hydrophobic). A mixture of water (a
polar liquid) and oil (a non-polar
liquid) will spontaneously separate into
two phases. Water has a very low
solubility (is insoluble) in oil, and oil
Iron-carbon phase diagram, showing the conditions necessary to form different phases
has a low solubility in water. Solubility
is the maximum amount of a solute
that can dissolve in a solvent before the solute ceases to dissolve and remains in a separate phase. A mixture can
separate into more than two liquid phases and the concept of phase separation extends to solids, i.e., solids can form
solid solutions or crystallize into distinct crystal phases. Metal pairs that are mutually soluble can form alloys,
whereas metal pair that are mutually insoluble cannot.
As many as eight immiscible liquid phases have been observed.[2] Mutually immiscible liquid phases are formed
from water (aqueous phase), hydrophobic organic solvents, perfluorocarbons (fluorous phase), silicones, several
different metals, and also from molten phosphorus. Not all organic solvents are completely miscible, e.g. a mixture
of ethylene glycol and toluene may separate into two distinct organic phases.[3]
Phases do not need to macroscopically separate spontaneously. Emulsions and colloids are examples of immiscible
phase pair combinations that do not physically separate.
Phase equilibrium
Left to equilibration, many compositions will form a uniform single phase, but depending on the temperature and
pressure even a single substance may separate into two or more distinct phases. Within each phase, the properties are
uniform but between the two phases properties differ.
Water in a closed jar with an air space over it forms a two phase system. Most of the water is in the liquid phase,
where it is held by the mutual attraction of water molecules. Even at equilibrium molecules are constantly in motion
and, once in a while, a molecule in the liquid phase gains enough kinetic energy to break away from the liquid phase
and enter the gas phase. Likewise, every once in a while a vapor molecule collides with the liquid surface and
condenses into the liquid. At equilibrium, evaporation and condensation processes exactly balance and there is no net
change in the volume of either phase.
At room temperature and pressure, the water jar reaches equilibrium when the air over the water has a humidity of
about 3%. This percentage increases as the temperature goes up. At 100 C and atmospheric pressure, equilibrium is
Phases
not reached until the air is 100% water. If the liquid is heated a little over 100 C, the transition from liquid to gas
will occur not only at the surface, but throughout the liquid volume: the water boils.
Number of phases
For a given composition, only certain phases are
possible at a given temperature and pressure.
The number and type of phases that will form is
hard to predict and is usually determined by
experiment. The results of such experiments can
be plotted in phase diagrams.
The phase diagram shown here is for a single
component system. In this simple system, which
phases that are possible depends only on
pressure and temperature. The markings show
points where two or more phases can co-exist in
equilibrium. At temperatures and pressures away
from the markings, there will be only one phase
at equilibrium.
A typical phase diagram for a single-component material, exhibiting solid,
In the diagram, the blue line marking the
liquid and gaseous phases. The solid green line shows the usual shape of the
boundary between liquid and gas does not
liquidsolid phase line. The dotted green line shows the anomalous behavior
continue indefinitely, but terminates at a point
of water.
called the critical point. As the temperature and
pressure approach the critical point, the properties of the liquid and gas become progressively more similar. At the
critical point, the liquid and gas become indistinguishable. Above the critical point, there are no longer separate
liquid and gas phases: there is only a generic fluid phase referred to as a supercritical fluid. In water, the critical point
occurs at around 647 K (374 C or 705 F) and 22.064 MPa.
An unusual feature of the water phase diagram is that the solidliquid phase line (illustrated by the dotted green line)
has a negative slope. For most substances, the slope is positive as exemplified by the dark green line. This unusual
feature of water is related to ice having a lower density than liquid water. Increasing the pressure drives the water
into the higher density phase, which causes melting.
Another interesting though not unusual feature of the phase diagram is the point where the solidliquid phase line
meets the liquidgas phase line. The intersection is referred to as the triple point. At the triple point, all three phases
can coexist.
Experimentally, the phase lines are relatively easy to map due to the interdependence of temperature and pressure
that develops when multiple phases forms. See Gibbs' phase rule. Consider a test apparatus consisting of a closed
and well insulated cylinder equipped with a piston. By charging the right amount of water and applying heat, the
system can be brought to any point in the gas region of the phase diagram. If the piston is slowly lowered, the system
will trace a curve of increasing temperature and pressure within the gas region of the phase diagram. At the point
where liquid begins to condense, the direction of the temperature and pressure curve will abruptly change to trace
along the phase line until all of the water has condensed.
177
Phases
Interfacial phenomena
Between two phases in equilibrium there is a narrow region where the properties are not that of either phase.
Although this region may be very thin, it can have significant and easily observable effects, such as causing a liquid
to exhibit surface tension. In mixtures, some components may preferentially move toward the interface. In terms of
modeling, describing, or understanding the behavior of a particular system, it may be efficacious to treat the
interfacial region as a separate phase.
Crystal phases
A single material may have several distinct solid states capable of forming separate phases. Water is a well known
example of such a material. For example, water ice is ordinarily found in the hexagonal form ice Ih, but can also
exist as the cubic ice Ic, the rhombohedral ice II, and many other forms. Polymorphism is the ability of a solid to
exist in more than one crystal form. For pure chemical elements, polymorphism is known as allotropy. For example,
diamond, graphite, and fullerenes are different allotropes of carbon.
Phase transitions
When a substance undergoes a phase transition (changes from one state of matter to another) it usually either takes
up or releases energy. For example, when water evaporates, the kinetic energy expended as the evaporating
molecules escape the attractive forces of the liquid is reflected in a decrease in temperature. The amount of energy
required to induce the transition is more than the amount required to heat the water from room temperature to just
short of boiling temperature, which is why evaporation is useful for cooling. See Enthalpy of vaporization. The
reverse process, condensation, releases heat. The heat energy, or enthalpy, associated with a solid to liquid transition
is the enthalpy of fusion and that associated with a solid to gas transition is the enthalpy of sublimation.
External links
French physicists find a solution that reversibly solidifies with a rise in temperature (http://physicsweb.org/
articles/news/8/9/15/1) -cyclodextrin, water, and 4-methylpyridine
178
Gas
179
Gas
Gas is one of the three classical states of matter (the others being liquid
and solid). Near absolute zero, a substance exists as a solid. As heat is
added to this substance it melts into a liquid at its melting point (see
phase change), boils into a gas at its boiling point, and if heated high
enough would enter a plasma state in which the electrons are so
energized that they leave their parent atoms from within the gas. A
pure gas may be made up of individual atoms (e.g. a noble gas or
atomic gas like neon), elemental molecules made from one type of
atom (e.g. oxygen), or compound molecules made from a variety of
Gas phase particles (atoms, molecules, or ions)
atoms (e.g. carbon dioxide). A gas mixture would contain a variety of
move around freely in the absence of an applied
electric field.
pure gases much like the air. What distinguishes a gas from liquids and
solids is the vast separation of the individual gas particles. This
separation usually makes a colorless gas invisible to the human observer. The interaction of gas particles in the
presence of electric and gravitational fields are considered negligible as indicated by the constant velocity vectors in
the image.
The gaseous state of matter is found between the liquid and plasma states,[1] the latter of which provides the upper
temperature boundary for gases. Bounding the lower end of the temperature scale lie degenerative quantum gases[2]
which are gaining increased attention these days.[3] High-density atomic gases super cooled to incredibly low
temperatures are classified by their statistical behavior as either a Bose gas or a Fermi gas. For a comprehensive
listing of these exotic states of matter see list of states of matter.
Etymology
The word gas is a neologism first used by the early 17th century Flemish chemist J.B. Van Helmont. Van Helmont's
word appears to have been simply a phonetic transcription of the Greek word Chaos the g in Dutch being
pronounced like the English ch in which case Van Helmont was simply following the established alchemical usage
first attested in the works of Paracelsus. According to Paracelsus's terminology, chaos meant something like
"ultra-rarified water".[4]
Physical characteristics
As most gases are difficult to observe directly with our senses, they
are described through the use of four physical properties or
macroscopic characteristics: pressure, volume, number of particles
(chemists group them by moles) and temperature. These four
characteristics were repeatedly observed by scientists such as
Robert Boyle, Jacques Charles, John Dalton, Joseph Gay-Lussac
and Amedeo Avogadro for a variety of gases in various settings.
Their detailed studies ultimately led to a mathematical relationship
among these properties expressed by the ideal gas law (see
simplified models section below).
Gas
180
Gas particles are widely separated from one another, and as such are not as strongly intermolecularly bonded to the
same degree as liquids or solids. These intermolecular forces result from electrostatic interactions between each gas
particle. Like charged areas of different gas particles repel, while oppositely charged regions of different gas
particles attract one another; gases that contain permanently charged ions are known as plasmas. Gaseous
compounds with polar covalent bonds contain permanent charge imbalances and so experience relatively strong
intermolecular forces, although the molecule while the compound's net charge remains neutral. Transient,
randomly-induced charges exist across non-polar covalent bonds of molecules and electrostatic interactions caused
by them are referred to as Van der Waals forces. The interaction of these intermolecular forces varies within a
substance which determines many of the physical properties unique to each gas.[5] [6] A quick comparison of boiling
points for compounds formed by ionic and covalent bonds leads us to this conclusion.[7] The drifting smoke particles
in the image provides some insight into low pressure gas behavior.
Compared to the other states of matter, gases have an incredibly low density and viscosity. Pressure and temperature
influence the particles within a certain volume. This variation in particle separation and speed is referred to as
compressibility. This particle separation and size influences optical properties of gases as can be found in the
following list of refractive indices. Finally, gas particles spread apart or diffuse in order to homogeneously distribute
themselves throughout any container.
Macroscopic
When observing a gas, it is typical to specify a frame of reference or
length scale. A larger length scale corresponds to a macroscopic or
global point of view of the gas. This region (referred to as a volume)
must be sufficient in size to contain a large sampling of gas particles.
The resulting statistical analysis of this sample size produces the
"average" behavior (i.e. velocity, temperature or pressure) of all the
gas particles within the region. By way of contrast, a smaller length
scale corresponds to a microscopic or particle point of view.
From this global vantage point, the gas characteristics measured are
Shuttle imagery of re-entry phase.
either in terms of the gas particles themselves (velocity, pressure, or
temperature) or their surroundings (volume). By way of example, Robert Boyle studied pneumatic chemistry for a
small portion of his career. One of his experiments related the macroscopic properties of pressure and volume of a
gas. His experiment used a J-tube manometer which looks like a test tube in the shape of the letter J. Boyle trapped
an inert gas in the closed end of the test tube with a column of mercury, thereby locking the number of particles and
temperature. He observed that when the pressure was increased on the gas, by adding more mercury to the column,
the trapped gas volume decreased. Mathematicians describe this situation as an inverse relationship. Furthermore,
when Boyle multiplied the pressure and volume of each observation, the product (math) was always the same, a
constant. This relationship held true for every gas that Boyle observed leading to the law, (PV=k), named to honor
his work in this field of study.
There are many math tools to choose from when analyzing gas properties. As gases are subjected to extreme
conditions, the math tools become a bit more complex, from the Euler equations (inviscid flow) to the Navier-Stokes
equations[8] that fully account for viscous effects. These equations are tailored to meet the unique conditions of the
gas system in question. Boyle's lab equipment allowed the use of algebra to obtain his analytical results. His results
were possible because he was studying gases in relatively low pressure situations where they behaved in an "ideal"
manner. These ideal relationships enable safety calculations for a variety of flight conditions on the materials in use.
The high technology equipment in use today was designed to help us safely explore the more exotic operating
environments where the gases no longer behave in an "ideal" manner. This advanced math, to include statistics and
Gas
181
multivariable calculus, makes possible the solution to such complex dynamic situations as space vehicle reentry. One
such example might be the analysis of the image depicting space shuttle reentry to ensure the material properties
under this loading condition are not exceeded. It is safe to say that in this flight regime, the gas is no longer behaving
ideally.
Pressure
The symbol used to represent pressure in equations is "p" or "P" with SI units of pascals.
When describing a container of gas, the term pressure (or absolute pressure) refers to the average force the gas exerts
on the surface area of the container. Within this volume, it is sometimes easier to visualize the gas particles moving
in straight lines until they collide with the container (see diagram at top of the article). The force imparted by a gas
particle into the container during this collision is the change in momentum of the particle. As a reminder from
classical mechanics, momentum, by definition, is the product of mass and velocity.[9] Notice that during a collision
only the normal component of velocity changes. A particle traveling parallel to the wall never changes its
momentum. So the average force on a surface must be the average change in linear momentum from all of these gas
particle collisions. To be more precise, pressure is the sum of all the normal components of force exerted by the
particles impacting the walls of the container divided by the surface area of the wall. The image "Pressurized gases"
depicts gas pressure and temperature spikes used in the entertainment industry.
Temperature
The symbol used to represent temperature in equations is T with SI units of kelvins.
The speed of a gas particle is proportional to its absolute temperature. The volume of the balloon in the video shrinks
when the trapped gas particles slow down with the addition of extremely cold nitrogen. The temperature of any
physical system is related to the motions of the particles (molecules and atoms) which make up the [gas] system.[10]
In statistical mechanics, temperature is the measure of the average kinetic energy stored in a particle. The methods of
storing this energy are dictated by the degrees of freedom of the particle itself (energy modes). Kinetic energy added
(endothermic process) to gas particles by way of collisions produces linear, rotational, and vibrational motion as
well. By contrast, a molecule in a solid can only increase its vibration modes with the addition of heat as the lattice
crystal structure prevents both linear and rotational motions. These heated gas molecules have a greater speed range
which constantly varies due to constant collisions with other particles. The speed range can be described by the
Maxwell-Boltzmann distribution. Use of this distribution implies ideal gases near thermodynamic equilibrium for the
system of particles being considered.
Specific volume
The symbol used to represent specific volume in equations is "v" with
SI units of cubic meters per kilogram.
The symbol used to represent volume in equations is "V" with SI units
of cubic meters.
When performing a thermodynamic analysis, it is typical to speak of
Expanding gases link to changes in specific
intensive and extensive properties. Properties which depend on the
volume.
amount of gas (either by mass or volume) are called extensive
properties, while properties that do not depend on the amount of gas are called intensive properties. Specific volume
is an example of an intensive property because it is the ratio of volume occupied by a unit of mass of a gas that is
identical throughout a system at equilibrium.[11] 1000 atoms of protactinium as a gas occupy the same space as any
other 1000 atoms for any given temperature and pressure. This concept is easier to visualize for solids such as iron
which are incompressible compared to gases. When the seat ejection is initiated in the rocket sled image the specific
Gas
182
volume increases with the expanding gases, while mass is conserved. Since a gas fills any container in which it is
placed, volume is an extensive property.
Density
The symbol used to represent density in equations is (pronounced rho) with SI units of kilograms per cubic meter.
This term is the reciprocal of specific volume.
Since gas molecules can move freely within a container, their mass is normally characterized by density. Density is
the mass per volume of a substance or simply, the inverse of specific volume. For gases, the density can vary over a
wide range because the particles are free to move closer together when constrained by pressure or volume or both.
This variation of density is referred to as compressibility. Like pressure and temperature, density is a state variable of
a gas and the change in density during any process is governed by the laws of thermodynamics. For a static gas, the
density is the same throughout the entire container. Density is therefore a scalar quantity; it is a simple physical
quantity that has a magnitude but no direction associated with it. It can be shown by kinetic theory that the density
is inversely proportional to the size of the container in which a fixed mass of gas is confined. In this case of a fixed
mass, the density decreases as the volume increases.
Microscopic
If one could observe a gas under a powerful microscope, one would see a collection of particles (molecules, atoms,
ions, electrons, etc.) without any definite shape or volume that are in more or less random motion. These neutral gas
particles only change direction when they collide with another particle or the sides of the container. By stipulating
that these collisions are perfectly elastic, this substance is transformed from a real to an ideal gas. This particle or
microscopic view of a gas is described by the Kinetic-molecular theory. All of the assumptions behind this theory
can be found in the postulates section of Kinetic Theory.
Kinetic theory
Kinetic theory provides insight into the macroscopic properties of gases by considering their molecular composition
and motion. Starting with the definitions of momentum and kinetic energy,[12] one can use the conservation of
momentum and geometric relationships of a cube to relate macro system properties of temperature and pressure to
the microscopic property of kinetic energy per molecule. The theory provides averaged values for these two
properties.
The theory also explains how the gas system responds to change. For example, as a gas is heated from absolute zero,
when it is (in theory) perfectly still, its internal energy (temperature) is increased. As a gas is heated, the particles
speed up and its temperature rise. This results in greater numbers of collisions with the container sides each second
due to the higher particle speeds associated with elevated temperatures. As the number of collisions (per unit time)
increase on the surface area of the container, the pressure increases in a proportional manner.
Gas
183
Brownian motion
Brownian motion is the mathematical model used to describe the
random movement of particles suspended in a fluid. The gas particle
animation, using pink and green particles, illustrates how this behavior
results in the spreading out of gases (entropy). These events are also
described by particle theory.
Since it is at the limit of (or beyond) current technology to observe
individual gas particles (atoms or molecules), only theoretical
calculations give suggestions as to how they move, but their motion is
different from Brownian Motion. The reason is that Brownian Motion
involves a smooth drag due to the frictional force of many gas
Random motion of gas particles results in
molecules, punctuated by violent collisions of an individual (or
diffusion.
several) gas molecule(s) with the particle. The particle (generally
consisting of millions or billions of atoms) thus moves in a jagged course, yet not so jagged as would be expected if
an individual gas molecule was examined.
Intermolecular forces
As discussed earlier, momentary attractions (or repulsions) between particles
have an effect on gas dynamics. In physical chemistry, the name given to these
intermolecular forces is van der Waals force. These forces play a key role in
determining physical properties of a gas such as viscosity and flow rate (see
physical characteristics section). Ignoring these forces in certain conditions
(see Kinetic-molecular theory) allows a real gas to be treated like an ideal gas.
This assumption allows the use of ideal gas laws which greatly simplifies the
path to a solution.
Proper use of these gas relationships requires us to take one more look at the
Kinetic-molecular theory (KMT). When these gas particles possess a magnetic
charge or Intermolecular force they gradually influence one another as the
spacing between them is reduced (the hydrogen bond model illustrates one
example). In the absence of any charge, at some point when the spacing between gas particles is greatly reduced they
can no longer avoid collisions between themselves at normal gas temperatures found in a lab. Another case for
increased collisions among gas particles would include a fixed volume of gas, which upon heating would contain
very fast particles. What this means to us is that these ideal equations provide reasonable results except for
extremely high pressure [compressible] or high temperature [ionized] conditions. Notice that all of these excepted
conditions allow energy transfer to take place within the gas system. The absence of these internal transfers is what
is referred to as ideal conditions (perfect or well behaved) in which the energy exchange occurs only at the
boundaries of the system. Real gases experience some of these collisions and intermolecular forces. When these
collisions are statistically negligible [incompressible], results from these ideal equations are still valid. At the other
end of the spectrum, when the gas particles are compressed into close proximity they behave more like a liquid, and
hence another connection to fluid dynamics.
When gases are compressed,
intermolecular forces like those shown
here start to play a more active role.
Gas
184
Simplified models
An equation of state (for gases) is a mathematical model used to roughly describe or predict the state properties of a
gas. At present, there is no single equation of state that accurately predicts the properties of all gases under all
conditions. Therefore, a number of much more accurate equations of state have been developed for gases in specific
temperature and pressure ranges. The "gas models" that are most widely discussed are "perfect gas", "ideal gas" and
"real gas". Each of these models has its own set of assumptions to facilitate the analysis of a given thermodynamic
system.[13] Each successive model expands the temperature range of coverage to which it applies. The image of first
powered flight at Kitty Hawk, North Carolina illustrates one example on the successful application of these
relationships in 1903. More recent examples include the 2009 maiden flights of the first solar powered aircraft, the
Solar Impulse, and the first commercial airliner to be constructed primarily from composite materials, the
Dreamliner.
where
is the specific gas constant for a particular gas, in units J/(kgK). This notation is the "gas dynamicist's"
version, which is more practical in modeling of gas flows involving acceleration without chemical reactions.
The ideal gas law does not make an assumption about the specific heat of a gas. In the most general case, the specific
heat is a function of both temperature and pressure. If the pressure-dependence is neglected (and possibly the
temperature-dependence as well) in a particular application, sometimes the gas is said to be a perfect gas, although
the exact assumptions may vary depending on the author and/or field of science.
For an ideal gas, the ideal gas law applies without restrictions on the specific heat. An ideal gas is a simplified "real
gas" with the assumption that the compressibility factor Z is set to 1 meaning that this pneumatic ratio remains
constant. A compressibility factor of one also requires the four state variables to follow the ideal gas law.
This approximation is more suitable for applications in engineering although simpler models can be used to produce
a "ball-park" range as to where the real solution should lie. An example where the "ideal gas approximation" would
be suitable would be inside a combustion chamber of a jet engine.[14] It may also be useful to keep the elementary
reactions and chemical dissociations for calculating emissions.
Gas
185
Real gas
Each one of the assumptions listed below adds to the complexity of the
problem's solution. As the density of a gas increases with pressure
rises, the intermolecular forces play a more substantial role in gas
behavior which results in the ideal gas law no longer providing
"reasonable" results. At the upper end of the engine temperature ranges
(e.g. combustor sections 1300 K), the complex fuel particles absorb
internal energy by means of rotations and vibrations that cause their
specific heats to vary from those of diatomic molecules and noble
21 April 1990 eruption of Mount Redoubt,
gases. At more than double that temperature, electronic excitation and
Alaska, illustrating real gases not in
dissociation of the gas particles begins to occur causing the pressure to
thermodynamic equilibrium.
adjust to a greater number of particles (transition from gas to
plasma).[15] Finally, all of the thermodynamic processes were
presumed to describe uniform gases whose velocities varied according to a fixed distribution. Using a
non-equilibrium situation implies the flow field must be characterized in some manner to enable a solution. One of
the first attempts to expand the boundaries of the ideal gas law was to include coverage for different thermodynamic
processes by adjusting the equation to read pVn = constant and then varying the n through different values such as
the specific heat ratio, .
Real gas effects include those adjustments made to account for a greater range of gas behavior:
For most applications, such a detailed analysis is excessive. Examples where "Real Gas effects" would have a
significant impact would be on the Space Shuttle re-entry where extremely high temperatures and pressures are
present or the gases produced during geological events as in the image of the 1990 eruption of Mount Redoubt.
Gas
186
Historical synthesis
Boyle's Law
Boyle's Law was perhaps the first expression of an equation of state.
In 1662 Robert Boyle performed a series of experiments employing
a J-shaped glass tube, which was sealed on one end. Mercury was
added to the tube, trapping a fixed quantity of air in the short, sealed
end of the tube. Then the volume of gas was carefully measured as
additional mercury was added to the tube. The pressure of the gas
could be determined by the difference between the mercury level in
the short end of the tube and that in the long, open end. Through
these experiments, Boyle noted that the gas volume varied inversely
with the pressure.[16] The image of Boyle's Equipment shows some
of the exotic tools used by Boyle during his study of gases.
Boyle's Law describes a gas in which the number of particles and
Temperature are constant.
PV = constant in this situation constant = nRT from the ideal gas law.
Law of volumes
Boyle's equipment.
In 1787, the French physicist and balloon pioneer, Jacques Charles, found
that oxygen, nitrogen, hydrogen, carbon dioxide, and air expand to the same extent over the same 80 kelvin interval.
In 1802, Joseph Louis Gay-Lussac published results of similar, though more extensive experiments, indicating a
linear relationship between volume and temperature. Gay-Lussac credited Charle's earlier work by naming the law in
his honor. In the absence of this linkage, Dalton could have been in contention for this honor for his previously
published work on partial pressures.
Law of Volumes Both Charles and Gay-Lussac played a role in developing this relationship.[17]
V/T = constant notice that constant = nR/P from the ideal gas law.
Avogadro's Law
In 1811, Amedeo Avogadro verified that equal volumes of pure gases
contain the same number of particles. His theory was not generally
accepted until 1858 when another Italian chemist Stanislao Cannizzaro
was able to explain non-ideal exceptions. For his work with gases a
century prior, the number that bears his name Avogadro's constant
represents the number of atoms found in 12grams of elemental
carbon-12 (6.0221023 mol1). This specific number of gas particles,
at standard temperature and pressure (ideal gas law) occupies 22.40
liters, which is referred to as the molar volume.
Avogadro's Law describes a gas in a container in which the
pressure and temperature are constant. The simplified form for the
ideal gas law follows:
V/n = constant notice that constant = RT/P from the ideal gas law.
Dalton's notation.
Gas
187
Dalton's Law
In 1801, John Dalton published the Law of Partial Pressures from his work with ideal gas law relationship: The
pressure of a mixture of gases is equal to the sum of the pressures of all of the constituent gases alone.
Mathematically, this can be represented for n species as:
Pressuretotal = Pressure1 + Pressure2 + ... + Pressuren
The image of Dalton's journal depicts symbology he used as shorthand to record the path he followed. Among his
key journal observations upon mixing unreactive "elastic fluids" (gases) were the following.[18] :
Unlike liquids, heavier gases did not drift to the bottom upon mixing.
Gas particle identity played no role in determining final pressure (they behaved as if their size was negligible).
Special topics
Compressibility
Thermodynamicists use this factor (Z) to alter the ideal gas equation to
account for compressibility effects of real gases. This factor represents
the ratio of actual to ideal specific volumes. It is sometimes referred to
as a "fudge-factor" or correction to expand the useful range of the ideal
gas law for design purposes. Usually this Z value is very close to unity.
The compressibility factor image illustrates how Z varies over a range
of very cold temperatures.
Compressibility factors for air.
Gas
188
Reynolds number
In fluid mechanics, the Reynolds number is the ratio of inertial forces (vs) to viscous forces (/L). It is one of the
most important dimensionless numbers in fluid dynamics and is used, usually along with other dimensionless
numbers, to provide a criterion for determining dynamic similitude. As such, the Reynolds number provides the link
between modeling results (design) and the full-scale actual conditions. It can also be used to characterize the flow.
Viscosity
Viscosity, a physical property, is a measure of how well adjacent
molecules stick to one another. A solid can withstand a shearing force
due to the strength of these sticky intermolecular forces. A fluid will
continuously deform when subjected to a similar load. While a gas has
a lower value of viscosity than a liquid, it is still an observable
property. If gases had no viscosity, then they would not stick to the
surface of a wing and form a boundary layer. A study of the delta wing
in the Schlieren image reveals that the gas particles stick to one another
(see Boundary layer section).
Gas
189
Turbulence
In fluid dynamics, turbulence or turbulent flow is a flow regime
characterized by chaotic, stochastic property changes. This includes
low momentum diffusion, high momentum convection, and rapid
variation of pressure and velocity in space and time. The Satellite view
of weather around Robinson Crusoe Islands illustrates just one
example.
Boundary layer
Particles will, in effect, "stick" to the surface of an object moving
through it. This layer of particles is called the boundary layer. At the
surface of the object, it is essentially static due to the friction of the
surface. The object, with its boundary layer is effectively the new
shape of the object that the rest of the molecules "see" as the object
Delta wing in wind tunnel. The shadows form as
approaches. This boundary layer can separate from the surface,
the indices of refraction change within the gas as
it compresses on the leading edge of this wing.
essentially creating a new surface and completely changing the flow
path. The classical example of this is a stalling airfoil. The delta wing
image clearly shows the boundary layer thickening as the gas flows from right to left along the leading edge.
Thermodynamic equilibrium
When energy transfer ceases from a system, this condition is referred to as thermodynamic equilibrium. Usually this
condition implies the system and surroundings are at the same temperature so that heat no longer transfers between
them. It also implies that external forces are balanced (volume does not change), and all chemical reactions within
the system are complete. The timeline varies for these events depending on the system in question. A container of ice
allowed to melt at room temperature takes hours, while in semiconductors the heat transfer that occurs in the device
transition from an on to off state could be on the order of a few nanoseconds.
Gas
190
Notes
[1] This early 20th century discussion infers what is regarded as the plasma state. See page 137 of American Chemical Society, Faraday Society,
Chemical Society (Great Britain) The Journal of physical chemistry, Volume 11 Cornell (1907).
[2] The work by T. Zelevinski provides another link to latest research about Strontium in this new field of study. See Tanya Zelevinsky (2009).
"84Srjust right for forming a Bose-Einstein condensate" (http:/ / physics. aps. org/ articles/ v2/ 94). Physics 2: 94. .
[3] for links material on the Bose-Einstein condensate see Quantum Gas Microscope Offers Glimpse Of Quirky Ultracold Atoms (http:/ / www.
sciencedaily. com/ releases/ 2009/ 11/ 091104140812. htm). ScienceDaily. 4 November 2009.
[4] Harper, Douglas. "gas" (http:/ / www. etymonline. com/ index. php?term=gas). Online Etymology Dictionary. .
[5] The authors make the connection between molecular forces of metals and their corresponding physical properties. By extension, this concept
would apply to gases as well, though not universally. Cornell (1907) pp. 1645.
[6] One noticeable exception to this physical property connection is conductivity which varies depending on the state of matter (ionic compounds
in water) as described by Michael Faraday in the 1833 when he noted that ice does not conduct a current. See page 45 of John Tyndall's
Faraday as a Discoverer (1868).
[7] John S. Hutchinson (2008). Concept Development Studies in Chemistry (http:/ / cnx. org/ content/ col10264/ latest/ ). p.67. .
[8] Anderson, p.501
[9] J. Clerk Maxwell (1904). Theory of Heat. Mineola: Dover Publications. pp.31920. ISBN0486417352.
[10] See pages 1378 of Society, Cornell (1907).
[11] Kenneth Wark (1977). Thermodynamics (3 ed.). McGraw-Hill. p.12. ISBN0-07-068280-1.
[12] For assumptions of Kinetic Theory see McPherson, pp.6061
[13] Anderson, pp. 289291
[14] John, p.205
[15]
[16]
[17]
[18]
References
Anderson, John D. (1984). Fundamentals of Aerodynamics. McGraw-Hill Higher Education. ISBN0070016569.
John, James (1984). Gas Dynamics. Allyn and Bacon. ISBN0-205-08014-6.
McPherson, William and Henderson, William (1917). An Elementary study of chemistry.
Further reading
Philip Hill and Carl Peterson. Mechanics and Thermodynamics of Propulsion: Second Edition Addison-Wesley,
1992. ISBN 0-201-14659-2
National Aeronautics and Space Administration (NASA). Animated Gas Lab (http://www.grc.nasa.gov/
WWW/K-12/airplane/Animation/frglab.html). Accessed February, 2008.
Georgia State University. HyperPhysics (http://hyperphysics.phy-astr.gsu.edu/hbase/hframe.html). Accessed
February, 2008.
Antony Lewis WordWeb (http://www.wordwebonline.com/en/GASEOUSSTATE). Accessed February, 2008.
Northwestern Michigan College The Gaseous State (http://www.nmc.edu/~bberthelsen/c9n03.htm). Accessed
February, 2008.
Liquid
Liquid
Liquid is one of the three classical states of matter (the others being gas and solid). Like a gas, a liquid is able to
flow and take the shape of a container. Some liquids resist compression, while others can be compressed. Unlike a
gas, a liquid does not disperse to fill every space of a container, and maintains a fairly constant density. A distinctive
property of the liquid state is surface tension, leading to wetting phenomena.
The density of a liquid is usually close to that of a solid, and much higher than in a gas. Therefore, liquid and solid
are both termed condensed matter. On the other hand, as liquids and gases share the ability to flow, they are both
called fluids.
Introduction
Liquid is one of the three primary states of
matter, with the others being solid and gas.
A liquid is a fluid. Unlike a solid, the
molecules in a liquid have a much greater
freedom to move. The forces that bind the
molecules together in a solid are only
temporary in a liquid, allowing a liquid to
flow while a solid remains rigid.
A liquid, like a gas, displays the properties
of a fluid. A liquid can flow, assume the
shape of a container, and, if placed in a
The formation of a spherical droplet of liquid water minimizes the surface area,
sealed container, will distribute applied
which is the natural result of surface tension in liquids.
pressure evenly to every surface in the
container. Unlike a gas, a liquid may not always mix readily with another liquid, will not always fill every space in
the container, forming its own surface, and will not compress significantly, except under extremely high pressures.
These properties make a liquid suitable for applications such as hydraulics.
Liquid particles are bound firmly but not rigidly. They are able to move around one another freely, resulting in a
limited degree of particle mobility. As the temperature increases, the increased vibrations of the molecules causes
distances between the molecules to increase. When a liquid reaches its boiling point, the cohesive forces that bind
the molecules closely together break, and the liquid changes to its gaseous state (unless superheating occurs). If the
temperature is decreased, the distances between the molecules become smaller. When the liquid reaches its freezing
point the molecules will usually lock into a very specific order, called crystallizing, and the bonds between them
become more rigid, changing the liquid into its solid state (unless supercooling occurs).
191
Liquid
Examples
Only two elements are liquid at room temperature and pressure: mercury and bromine. Five more elements have
melting points slightly above room temperature: francium, caesium, gallium and rubidium.[1] Metal alloys that are
liquid at room temperature include NaK, a sodium-potassium metal alloy, galinstan, a fusible alloy liquid, and some
amalgams (alloys involving mercury).
Pure substances that are liquid under normal conditions include water, ethanol and many other organic solvents.
Liquid water is of vital importance in chemistry and biology; it is believed to be a necessity for the existence of life.
Important everyday liquids include aqueous solutions like household bleach, other mixtures of different substances
such as mineral oil and gasoline, emulsions like vinaigrette or mayonnaise, suspensions like blood, and colloids like
paint and milk.
Many gases can be liquefied by cooling, producing liquids such as liquid oxygen, liquid nitrogen, liquid hydrogen
and liquid helium. Not all gases can be liquified at atmospheric pressure, for example carbon dioxide can only be
liquified at pressures above 5.1 atm.
Some materials cannot be classified within the classical three states of matter; they possess solid-like and liquid-like
properties. Examples include liquid crystals, used in LCD displays, and biological membranes.
Applications
Liquids have a variety of uses, as lubricants, solvents, and coolants. In hydraulic systems, liquid is used to transmit
power.
In tribology, liquids are studied for their properties as lubricants. Lubricants such as oil are chosen for viscosity and
flow characteristics that are suitable throughout the operating temperature range of the component. Oils are often
used in engines, gear boxes, metalworking, and hydraulic systems for their good lubrication properties.[2]
Many liquids are used as solvents, to dissolve other liquids or solids. Solutions are found in a wide variety of
applications, including paints, sealants, and adhesives. Naptha and acetone are used frequently in industry to clean
oil, grease, and tar from parts and machinery. Body fluids are water based solutions.
Surfactants are commonly found in soaps and detergents. Solvents like alcohol are often used as antimicrobials.
They are found in cosmetics, inks, and liquid dye lasers. They are used in the food industry, in processes such as the
extraction of vegetable oil.[3]
Liquids tend to have better thermal conductivity than gases, and the ability to flow makes a liquid suitable for
removing excess heat from mechanical components. The heat can be removed by channeling the liquid through a
heat exchanger, such as a radiator, or the heat can be removed with the liquid during evaporation.[4] Water or glycol
coolants are used to keep engines from overheating.[5] The coolants used in nuclear reactors include water or liquid
metals, such as sodium or bismuth.[6] Liquid propellant films are used to cool the thrust chambers of rockets.[7] In
machining, water and oils are used to remove the excess heat generated, which can quickly ruin both the work piece
and the tooling. During perspiration, sweat removes heat from the human body by evaporating. In the heating,
ventilation, and air-conditioning industry (HVAC), liquids such as water are used to transfer heat from one area to
another.[8]
Liquid is the primary component of hydraulic systems, which take advantage of Pascal's law to provide fluid power.
Devices such as pumps and waterwheels have been used to change liquid motion into mechanical work since ancient
times. Oils are forced through hydraulic pumps, which transmit this force to hydraulic cylinders. Hydraulics can be
found in many applications, such as automotive brakes and transmissions, heavy equipment, and airplane control
systems. Various hydraulic presses are used extensively in repair and manufacturing, for lifting, pressing, clamping
and forming.[9]
192
Liquid
193
Liquids are sometimes used in measuring devices. A thermometer often uses the thermal expansion of liquids, such
as mercury, combined with their ability to flow to indicate temperature. A manometer uses the weight of the liquid to
indicate air pressure.[10]
Mechanical Properties
Volume
Quantities of liquids are commonly measured in units of volume. These include the SI unit cubic metre (m3) and its
divisions, in particular the cubic decimetre, more commonly called the litre (1 dm3 = 1 L = 0.001 m3), and the cubic
centimetre, also called millilitre (1cm3 = 1 mL = 0.001 L = 106 m3).
The volume of a quantity of liquid is fixed by its temperature and pressure. Liquids generally expand when heated,
and contract when cooled. Water between 0C and 4C is a notable exception. Liquids have little compressibility:
water, for example, requires a pressure of the order of 200 bar to increase its density by 1/1000. In the study of fluid
dynamics, liquids are often treated as incompressible, especially when studying incompressible flow.
where:
is the density of the liquid (assumed constant)
is the gravitational acceleration.
Note that this formula assumes that the pressure at the free surface is zero, and that surface tension effects may be
neglected.
Objects immersed in liquids are subject to the phenomenon of buoyancy. (Buoyancy is also observed in other fluids,
but is especially strong in liquids due to their high density.)
Surfaces
Unless the volume of a liquid exactly matches the
volume of its container, one or more surfaces are
observed. The surface of a liquid behaves like an elastic
membrane in which surface tension appears, allowing
the formation of drops and bubbles. Surface waves,
capillary action, wetting, and ripples are other
consequences of surface tension.
Flow
Viscosity measures the resistance of a liquid which is
being deformed by either shear stress or extensional
stress.
When a liquid is supercooled towards the glass transition, the viscosity increases dramatically. The liquid then
becomes a viscoelastic medium that shows both the elasticity of a solid and the fluidity of a liquid, depending on the
time scale of observation or on the frequency of perturbation.
Liquid
Sound propagation
In a fluid the only non-zero stiffness is to volumetric deformation (a fluid does not sustain shear forces). Hence the
speed of sound in a fluid is given by
where K is the bulk modulus of the fluid, and the density. To
give a typical value, in fresh water c=1497m/s at 25C.
Thermodynamics
Phase transitions
At a temperature below the boiling point,
any matter in liquid form will evaporate
until the condensation of gas above reach an
equilibrium. At this point the gas will
condense at the same rate as the liquid
evaporates. Thus, a liquid cannot exist
permanently if the evaporated liquid is
continually removed. A liquid at its boiling
point will evaporate more quickly than the
gas can condense at the current pressure. A
liquid at or above its boiling point will
normally boil, though superheating can
prevent this in certain circumstances.
At a temperature below the freezing point, a
liquid will tend to crystallize, changing to its
A typical phase diagram. The dotted line gives the anomalous behaviour of water.
solid form. Unlike the transition to gas,
The green lines show how the freezing point can vary with pressure, and the blue
there is no equilibrium at this transition
line shows how the boiling point can vary with pressure. The red line shows the
under constant pressure, so unless
boundary where sublimation or deposition can occur.
supercooling occurs, the liquid will
eventually completely crystallize. Note that
this is only true under constant pressure, so e.g. water and ice in a closed, strong container might reach an
equilibrium where both phases coexist. For the opposite transition from solid to liquid, see melting.
Solutions
Liquids can display immiscibility. The most familiar mixture of two immiscible liquids in everyday life is the
vegetable oil and water in Italian salad dressing. A familiar set of miscible liquids is water and alcohol. Liquid
components in a mixture can often be separated from one another via fractional distillation.
194
Liquid
195
Microscopic Properties
Static structure factor
In a liquid, atoms do not form a crystalline lattice, nor do they
show any other form of long-range order. This is evidenced by the
absence of Bragg peaks in X-ray and neutron diffraction. Under
normal conditions, the diffraction pattern has circular symmetry,
expressing the isotropy of the liquid. In radial direction, the
diffraction intensity smoothly oscillates. This is usually described
by the static structure factor S(q), with wavenumber q=(4/)sin
given by the wavelength of the probe (photon or neutron) and the
Bragg angle . The oscillations of S(q) express the near order of
the liquid, i.e. the correlations between an atom and a few shells of
nearest, second nearest, ... neighbors.
A more intuitive description of these correlations is given by the radial distribution function g(r), which is basically
the Fourier transform of S(q). It represents a spatial average of a temporal snapshot of pair correlations in the liquid.
independent then the liquid behaves as a linear medium, so that sound propagates without dissipation and without
mode coupling. In reality, any liquid shows some dispersion: with increasing frequency, K crosses over from the
low-frequency, liquid-like limit
to the high-frequency, solid-like limit
. In normal liquids, most of this
cross over takes place at frequencies between GHz and THz, sometimes called hypersound.
At sub-GHz frequencies, a normal liquid cannot sustain shear waves: the zero-frequency limit of the shear modulus
is
. This is sometimes seen as the defining property of a liquid.[11] However, just as the bulk modulus K,
the shear modulus G is frequency dependent, and at hypersound frequencies it shows a similar cross over from the
liquid-like limit
to a solid-like, non-zero limit
.
According to the Kramers-Kronig relation, the dispersion in the sound velocity (given by the real part of K or G)
goes along with a maximum in the sound attenuation (dissipation, given by the imaginary part of K or G). According
Liquid
to linear response theory, the Fourier transform of K or G describes how the system returns to equilibrium after an
external perturbation; for this reason, the dispersion step in the GHz..THz region is also called structural relaxation.
According the fluctuation-dissipation theorem, relaxation towards equilibrium is intimately connected to fluctuations
in equilibrium. The density fluctuations associated with sound waves can be experimentally observed by Brillouin
scattering.
On supercooling a liquid towards the glass transition, the crossover from liquid-like to solid-like response moves
from GHz to MHz, kHz, Hz, ...; equivalently, the characteristic time of structural relaxation increases from ns to s,
ms, s, ... This is the microscopic explanation for the above mentioned viscoelastic behaviour of glass-forming
liquids.
Effects of association
The mechanisms of atomic/molecular diffusion (or particle displacement) in solids are closely related to the
mechanisms of viscous flow and solidification in liquid materials. Descriptions of viscosity in terms of molecular
"free space" within the liquid[12] were modified as needed in order to account for liquids whose molecules are known
to be "associated" in the liquid state at ordinary temperatures. When various molecules combine together to form an
associated molecule, they enclose within a semi-rigid system a certain amount of space which before was available
as free space for mobile molecules. Thus, increase in viscosity upon cooling due to the tendency of most substances
to become associated on cooling.[13]
Similar arguments could be used to describe the effects of pressure on viscosity, where it may be assumed that the
viscosity is chiefly a function of the volume for liquids with a finite compressibility. An increasing viscosity with
rise of pressure is therefore expected. In addition, if the volume is expanded by heat but reduced again by pressure,
the viscosity remains the same.
The local tendency to orientation of molecules in small groups lends the liquid (as referred to previously) a certain
degree of association. This association results in a considerable "internal pressure" within a liquid, which is due
almost entirely to those molecules which, on account of their temporary low velocities (following the Maxwell
distribution) have coalesced with other molecules. The internal pressure between several such molecules might
correspond to that between a group of molecules in the solid form.
References
[1] Theodore Gray, The Elements: A Visual Exploration of Every Known Atom in the Universe New York: Workman Publishing, 2009 p. 127
ISBN 1579128149
[2] Theo Mang, Wilfried Dressel Lubricants and lubrication (http:/ / books. google. com/ books?id=UTdfxf2rkNcC& ), Wiley-VCH 2007
ISBN 3527314970
[3] George Wypych Handbook of solvents (http:/ / books. google. com/ books?id=NzhUTvUkpDQC& pg=PA847) William Andrew
Publishing 2001 pp. 847-881 ISBN 1895198240
[4] N. B. Vargaftik Handbook of thermal conductivity of liquids and gases CRC Press 1994 ISBN 0849393450
[5] Jack Erjavec Automotive technology: a systems approach (http:/ / books. google. com/ books?id=U4TBoJB2zgsC& pg=PA309) Delmar
Learning 2000 p. 309 ISBN 1401848311
[6] Gerald Wendt The prospects of nuclear power and technology D. Van Nostrand Company 1957 p. 266
[7] Modern engineering for design of liquid-propellant rocket engines by Dieter K. Huzel, David H. Huang American Institute of
Aeronautics and Astronautics 1992 p. 99 ISBN 1563470136
[8] Thomas E Mull HVAC principles and applications manual McGraw-Hill 1997 ISBN 007044451X
[9] R. Keith Mobley Fluid power dynamics (http:/ / books. google. com/ books?id=8DyLdlfJzoMC& pg=PA1) Butterworth-Heinemann 2000 p.
vii ISBN 0750671742
[10] Bela G. Liptak Instrument engineers handbook: process control (http:/ / books. google. com/ books?id=pPMursVsxlMC& pg=PA807)
CRC Press 1999 p. 807 ISBN 0849310814
[11] Born, M., The Stability of Crystal Lattices, Proc. Camb. Phil. Soc., Vol. 36, p.160, (1940) doi=10.1017/S0305004100017138;
Thermodynamics of Crystals and Melting, J. Chem. Phys., Vol. 7, p. 591 (1939) doi=10.1063/1.1750497; A General Kinetic Theory of
Liquids, University Press (1949)
196
Liquid
197
[12] D.B. Macleod (1923). "On a relation between the viscosity of a liquid and its coefficient of expansion". Trans. Farad. Soc. 19: 6.
doi:10.1039/tf9231900006.
[13] G.W Stewart (1930). "The Cybotactic (Molecular Group) Condition in Liquids; the Association of Molecules". Phys. Rev. 35 (7): 726.
Bibcode1930PhRv...35..726S. doi:10.1103/PhysRev.35.726.
Solid
Solid is one of the three classical states of
matter (the others being gas and liquid). It is
characterized by structural rigidity and
resistance to changes of shape or volume.
Unlike a liquid, a solid object does not flow
to take on the shape of its container, nor
does it expand to fill the entire volume
available to it like a gas does. The atoms in
a solid are tightly bound to each other, either
in a regular geometric lattice (crystalline
solids, which include metals and ordinary
water ice) or irregularly (an amorphous solid
such as common window glass).
Single crystalline form of solid Insulin.
Solid
198
Microscopic description
The atoms, molecules or ions which make up a solid may be arranged
in an orderly repeating pattern, or irregularly. Materials whose
constituents are arranged in a regular pattern are known as crystals. In
some cases, the regular ordering can continue unbroken over a large
scale, for example diamonds, where each diamond is a single crystal.
Solid objects that are large enough to see and handle are rarely
composed of a single crystal, but instead are made of a large number of
single crystals, known as crystallites, whose size can vary from a few
nanometers to several meters. Such materials are called polycrystalline.
Almost all common metals, and many ceramics, are polycrystalline.
Solid
199
In other materials, there is no long-range order in the position of the atoms. These solids are known as amorphous
solids; examples include polystyrene and glass.
Whether a solid is crystalline or amorphous depends on the material involved, and the conditions in which it was
formed. Solids which are formed by slow cooling will tend to be crystalline, while solids which are frozen rapidly
are more likely to be amorphous. Likewise, the specific crystal structure adopted by a crystalline solid depends on
the material involved and on how it was formed.
While many common objects, such as an ice cube or a coin, are chemically identical throughout, many other
common materials comprise a number of different substances packed together. For example, a typical rock is an
aggregate of several different minerals and mineraloids, with no specific chemical composition. Wood is a natural
organic material consisting primarily of cellulose fibers embedded in a matrix of organic lignin. In materials science,
composites of more than one constituent material can be designed to have desired properties.
Classes of solids
Further information: Bonding in solids
The forces between the atoms in a solid can take a variety of forms. For example, a crystal of sodium chloride
(common salt) is made up of ionic sodium and chlorine, which are held together by ionic bonds. In diamond or
silicon, the atoms share electrons and form covalent bonds. In metals, electrons are shared in metallic bonding. Some
solids, particularly most organic compounds, are held together with van der Waals forces resulting from the
polarization of the electronic charge cloud on each molecule. The dissimilarities between the types of solid result
from the differences between their bonding.
Metals
Metals typically are strong, dense, and good conductors of both
electricity and heat. The bulk of the elements in the periodic table,
those to the left of a diagonal line drawn from boron to polonium, are
metals. Mixtures of two or more elements in which the major
component is a metal are known as alloys.
People have been using metals for a variety of purposes since
prehistoric times. The strength and reliability of metals has led to their
widespread use in construction of buildings and other structures, as
well as in most vehicles, many appliances and tools, pipes, road signs
and railroad tracks. Iron and aluminium are the two most commonly
used structural metals, and they are also the most abundant metals in
the Earth's crust. Iron is most commonly used in the form of an alloy,
steel, which contains up to 2.1% carbon, making it much harder than
pure iron.
Because metals are good conductors of electricity, they are valuable in
electrical appliances and for carrying an electric current over long
Solid
200
distances with little energy loss or dissipation. Thus, electrical power grids rely on metal cables to distribute
electricity. Home electrical systems, for example, are wired with copper for its good conducting properties and easy
machinability. The high thermal conductivity of most metals also makes them useful for stovetop cooking utensils.
The study of metallic elements and their alloys makes up a significant portion of the fields of solid-state chemistry,
physics, materials science and engineering.
Metallic solids are held together by a high density of shared, delocalized electrons, known as "metallic bonding". In
a metal, atoms readily lose their outermost ("valence") electrons, forming positive ions. The free electrons are spread
over the entire solid, which is held together firmly by electrostatic interactions between the ions and the electron
cloud.[1] The large number of free electrons gives metals their high values of electrical and thermal conductivity. The
free electrons also prevent transmission of visible light, making metals opaque, shiny and lustrous.
More advanced models of metal properties consider the effect of the positive ions cores on the delocalised electrons.
As most metals have crystalline structure, those ions are usually arranged into a periodic lattice. Mathematically, the
potential of the ion cores can be treated by various models, the simplest being the nearly free electron model.
Minerals
Minerals are naturally occurring solids formed through various
geological processes under high pressures. To be classified as a true
mineral, a substance must have a crystal structure with uniform
physical properties throughout. Minerals range in composition from
pure elements and simple salts to very complex silicates with
thousands of known forms. In contrast, a rock sample is a random
aggregate of minerals and/or mineraloids, and has no specific chemical
composition. The vast majority of the rocks of the Earth's crust consist
of quartz (crystalline SiO2), feldspar, mica, chlorite, kaolin, calcite,
A collection of various minerals.
epidote, olivine, augite, hornblende, magnetite, hematite, limonite and
a few other minerals. Some minerals, like quartz, mica or feldspar are
common, while others have been found in only a few locations worldwide. The largest group of minerals by far is
the silicates (most rocks are 95% silicates), which are composed largely of silicon and oxygen, with the addition of
ions of aluminium, magnesium, iron, calcium and other metals.
Ceramics
Ceramic solids are composed of inorganic compounds, usually oxides
of chemical elements. They are chemically inert, and often are capable
of withstanding chemical erosion that occurs in an acidic or caustic
environment. Ceramics generally can withstand high temperatures
ranging from 1000 to 1600 C (1800 to 3000 F). Exceptions include
non-oxide inorganic materials, such as nitrides, borides and carbides.
Traditional ceramic raw materials include clay minerals such as
kaolinite, more recent materials include aluminium oxide (alumina).
The modern ceramic materials, which are classified as advanced
ceramics, include silicon carbide and tungsten carbide. Both are valued
for their abrasion resistance, and hence find use in such applications as
the wear plates of crushing equipment in mining operations.
Most ceramic materials, such as alumina and its compounds, are formed from fine powders, yielding a fine grained
polycrystalline microstructure which is filled with light scattering centers comparable to the wavelength of visible
Solid
light. Thus, they are generally opaque materials, as opposed to transparent materials. Recent nanoscale (e.g. sol-gel)
technology has, however, made possible the production of polycrystalline transparent ceramics such as transparent
alumina and alumina compounds for such applications as high-power lasers. Advanced ceramics are also used in the
medicine, electrical and electronics industries.
Ceramic engineering is the science and technology of creating solid-state ceramic materials, parts and devices. This
is done either by the action of heat, or, at lower temperatures, using precipitation reactions from chemical solutions.
The term includes the purification of raw materials, the study and production of the chemical compounds concerned,
their formation into components, and the study of their structure, composition and properties.
Mechanically speaking, ceramic materials are brittle, hard, strong in compression and weak in shearing and tension.
Brittle materials may exhibit significant tensile strength by supporting a static load. Toughness indicates how much
energy a material can absorb before mechanical failure, while fracture toughness (denoted KIc ) describes the ability
of a material with inherent microstructural flaws to resist fracture via crack growth and propagation. If a material has
a large value of fracture toughness, the basic principles of fracture mechanics suggest that it will most likely undergo
ductile fracture. Brittle fracture is very characteristic of most ceramic and glass-ceramic materials which typically
exhibit low (and inconsistent) values of KIc.
For example of applications of ceramics, the extreme hardness of Zirconia is utilized in the manufacture of knife
blades, as well as other industrial cutting tools. Ceramics such as alumina, boron carbide and silicon carbide have
been used in bulletproof vests to repel large-caliber rifle fire. Silicon nitride parts are used in ceramic ball bearings,
where their high hardness makes them wear resistant. In general, ceramics are also chemically resistant and can be
used in wet environments where steel bearings would be susceptible to oxidation (or rust).
As another example of ceramic applications, in the early 1980s, Toyota
researched production of an adiabatic ceramic engine with an operating
temperature of over 6000 F (3300 C). Ceramic engines do not require
a cooling system and hence allow a major weight reduction and
therefore greater fuel efficiency. In a conventional metallic engine,
much of the energy released from the fuel must be dissipated as waste
heat in order to prevent a meltdown of the metallic parts. Work is also
being done in developing ceramic parts for gas turbine engines.
Turbine engines made with ceramics could operate more efficiently,
Radial rotor made from Si3N4 for a gas turbine
giving aircraft greater range and payload for a set amount of fuel.
engine
However, such engines are not in production because the
manufacturing of ceramic parts in the sufficient precision and
durability is difficult and costly. Processing methods often result in a wide distribution of microscopic flaws which
frequently play a detrimental role in the sintering process, resulting in the proliferation of cracks, and ultimate
mechanical failure.
201
Solid
202
Glass ceramics
Glass-ceramic materials share many properties with both
non-crystalline glasses and crystalline ceramics. They are formed as a
glass, and then partially crystallized by heat treatment, producing both
amorphous and crystalline phases so that crystalline grains are
embedded within a non-crystalline intergranular phase.
Glass-ceramics are used to make cookware (originally known by the
brand name CorningWare) and stovetops which have both high
resistance to thermal shock and extremely low permeability to liquids.
A high strength glass-ceramic cooktop with
The negative coefficient of thermal expansion of the crystalline
negligible thermal expansion.
ceramic phase can be balanced with the positive coefficient of the
glassy phase. At a certain point (~70% crystalline) the glass-ceramic has a net coefficient of thermal expansion close
to zero. This type of glass-ceramic exhibits excellent mechanical properties and can sustain repeated and quick
temperature changes up to 1000C.
Glass ceramics may also occur naturally when lightning strikes the crystalline (e.g. quartz) grains found in most
beach sand. In this case, the extreme and immediate heat of the lightning (~2500 C) creates hollow, branching
rootlike structures called fulgurite via fusion.
Organic solids
Organic chemistry studies the structure, properties,
composition, reactions, and preparation by synthesis (or
other means) of chemical compounds of carbon and
hydrogen, which may contain any number of other
elements such as nitrogen, oxygen and the halogens:
fluorine, chlorine, bromine and iodine. Some organic
compounds may also contain the elements phosphorus
or sulfur. Examples of organic solids include wood,
paraffin wax, naphthalene and a wide variety of
polymers and plastics.
Wood
The individual wood pulp fibers in this sample are around 10 m in
Solid
203
Polymers
One important property of carbon in organic chemistry is that it can
form certain compounds, the individual molecules of which are
capable of attaching themselves to one another, thereby forming a
chain or a network. The process is called polymerization and the chains
or networks polymers, while the source compound is a monomer. Two
main groups of polymers exist: those artificially manufactured are
referred to as industrial polymers or synthetic polymers (plastics) and
those naturally occurring as biopolymers.
STM image of self-assembled supramolecular
Composite materials
Composite materials contain two or more macroscopic
phases, one of which is often ceramic. For example, a
continuous matrix, and a dispersed phase of ceramic
particles or fibers.
Applications of composite materials range from
structural elements such as steel-reinforced concrete, to
the thermally insulative tiles which play a key and
integral role in NASA's Space Shuttle thermal
protection system which is used to protect the surface
of the shuttle from the heat of re-entry into the Earth's
atmosphere.
One
example
is
Reinforced
Solid
204
Semiconductors
Semiconductors are materials that have an electrical resistivity (and
conductivity) between that of metallic conductors and non-metallic
insulators. They can be found in the periodic table moving diagonally
downward right from boron. They separate the electrical conductors
(or metals, to the left) from the insulators (to the right).
Devices made from semiconductor materials are the foundation of
modern electronics, including radio, computers, telephones, etc.
Semiconductor devices include the transistor, solar cells, diodes and
integrated circuits. Solar photovoltaic panels are large semiconductor
devices that directly convert light into electrical energy.
In a metallic conductor, current is carried by the flow of electrons", but in semiconductors, current can be carried
either by electrons or by the positively charged "holes" in the electronic band structure of the material. Common
semiconductor materials include silicon, germanium and gallium arsenide.
Solid
205
Nanomaterials
Many traditional solids exhibit different properties when they shrink to
nanometer sizes. For example, nanoparticles of usually yellow gold
and gray silicon are red in color; gold nanoparticles melt at much lower
temperatures (~300 C for 2.5nm size) than the gold slabs (1064
C);[2] and metallic nanowires are much stronger than the
corresponding bulk metals.[3] [4] The high surface area of nanoparticles
makes them extremely attractive for certain applications in the field of
energy. For example, platinum metals may be provide improvements
as automotive fuel catalysts, as well as proton exchange membrane
(PEM) fuel cells. Also, ceramic oxides (or cermets) of lanthanum,
Bulk silicon (left) and silicon nanopowder (right)
cerium, manganese and nickel are now being developed as solid oxide
fuel cells (SOFC). Lithium, lithiumtitanate and tantalum nanoparticles are being applied in lithium ion batteries.
Silicon nanoparticles have been shown to dramatically expand the storage capacity of lithium ion batteries during the
expansion/contraction cycle. Silicon nanowires cycle without significant degradation and present the potential for
use in batteries with greatly expanded storage times. Silicon nanoparticles are also being used in new forms of solar
energy cells. Thin film deposition of silicon quantum dots on the polycrystalline silicon substrate of a photovoltaic
(solar) cell increases voltage output as much as 60% by fluorescing the incoming light prior to capture. Here again,
surface area of the nanoparticles (and thin films) plays a critical role in maximizing the amount of absorbed
radiation.
Biomaterials
Many natural (or biological) materials are complex
composites with remarkable mechanical properties.
These complex structures, which have risen from
hundreds of million years of evolution, are inspiring
materials scientists in the design of novel materials.
Their defining characteristics include structural
hierarchy,
multifunctionality
and
self-healing
capability. Self-organization is also a fundamental
feature of many biological materials and the manner by
which the structures are assembled from the molecular
level up. Thus, self-assembly is emerging as a new
strategy in the chemical synthesis of high performance
biomaterials.
Physical properties
Physical properties of elements and compounds which provide conclusive evidence of chemical composition include
odor, color, volume, density (mass per unit volume), melting point, boiling point, heat capacity, physical form and
shape at room temperature (solid, liquid or gas; cubic, trigonal crystals, etc.), hardness, porosity, index of refraction
and many others. This section discusses some physical properties of materials in the solid state.
Solid
206
Mechanical
The mechanical properties of materials
describe characteristics such as their
strength and resistance to deformation. For
example, steel beams are used in
construction because of their high strength,
meaning that they neither break nor bend
significantly under the applied load.
Mechanical properties include elasticity and
plasticity, tensile strength, compressive
strength, shear strength, fracture toughness,
ductility (low in brittle materials), and
indentation hardness. Solid mechanics is the
study of the behavior of solid matter under
external actions such as external forces and
temperature changes.
Granite rock formation in the Chilean Patagonia. Like most inorganic minerals
formed by oxidation in the Earth's atmosphere, granite consists primarily of
crystalline silica SiO2 and alumina Al2O3.
Solid
207
Thermal
Because solids have thermal energy, their atoms vibrate
about fixed mean positions within the ordered (or
disordered) lattice. The spectrum of lattice vibrations in
a crystalline or glassy network provides the foundation
for the kinetic theory of solids. This motion occurs at
the atomic level, and thus cannot be observed or
detected without highly specialized equipment, such as
that used in spectroscopy.
Thermal properties of solids include thermal
conductivity, which is the property of a material that
indicates its ability to conduct heat. Solids also have a
specific heat capacity, which is the capacity of a
material to store energy in the form of heat (or thermal
lattice vibrations).
Electrical
Solid
Optical
Materials can transmit (e.g. glass) or reflect (e.g. metals) visible light.
Many materials will transmit some wavelengths while blocking others. For example, window glass is transparent to
visible light, but much less so to most of the frequencies of ultraviolet light that cause sunburn. This property is used
for frequency-selective optical filters, which can alter the color of incident light.
For some purposes, both the optical and mechanical properties of a material can be of interest. For example, the
sensors on an infrared homing ("heat-seeking") missile must be protected by a cover which is transparent to infrared
radiation. The current material of choice for high-speed infrared-guided missile domes is single-crystal sapphire. The
optical transmission of sapphire does not actually extend to cover the entire mid-infrared range (35m), but starts
to drop off at wavelengths greater than approximately 4.5m at room temperature. While the strength of sapphire is
better than that of other available mid-range infrared dome materials at room temperature, it weakens above 600 C.
A long standing trade-off exists between optical bandpass and mechanical durability; new materials such as
transparent ceramics or optical nanocomposites may provide improved performance.
Guided lightwave transmission involves the field of fiber optics and the ability of certain glasses to transmit,
simultaneously and with low loss of intensity, a range of frequencies (multi-mode optical waveguides) with little
interference between them. Optical waveguides are used as components in integrated optical circuits or as the
transmission medium in optical communication systems.
Opto-electronic
A solar cell or photovoltaic cell is a device that converts light energy into electrical energy. Fundamentally, the
device needs to fulfill only two functions: photo-generation of charge carriers (electrons and holes) in a
light-absorbing material, and separation of the charge carriers to a conductive contact that will transmit the electricity
(simply put, carrying electrons off through a metal contact into an external circuit). This conversion is called the
photoelectric effect, and the field of research related to solar cells is known as photovoltaics.
Solar cells have many applications. They have long been used in situations where electrical power from the grid is
unavailable, such as in remote area power systems, Earth-orbiting satellites and space probes, handheld calculators,
wrist watches, remote radiotelephones and water pumping applications. More recently, they are starting to be used in
assemblies of solar modules (photovoltaic arrays) connected to the electricity grid through an inverter, that is not to
act as a sole supply but as an additional electricity source.
All solar cells require a light absorbing material contained within the cell structure to absorb photons and generate
electrons via the photovoltaic effect. The materials used in solar cells tend to have the property of preferentially
absorbing the wavelengths of solar light that reach the earth surface. However, some solar cells are optimized for
light absorption beyond Earth's atmosphere as well.
References
[1] Mortimer, Charles E. (1975). Chemistry: A Conceptual Approach (3rd ed.). New York:: D. Van Nostrad Company. ISBN0442255454.
[2] Buffat, Ph.; Borel, J.-P. (1976). "Size effect on the melting temperature of gold particles". Physical Review A 13 (6): 2287.
Bibcode1976PhRvA..13.2287B. doi:10.1103/PhysRevA.13.2287.
[3] Walter H. Kohl (1995). Handbook of materials and techniques for vacuum devices (http:/ / books. google. com/ ?id=-Ll6qjWB-RUC&
pg=PA164). Springer. pp.164167. ISBN1563963876. .
[4] Shpak, Anatoly P; Kotrechko, Sergiy O; Mazilova, Tatjana I; Mikhailovskij, Igor M (2009). "Inherent tensile strength of molybdenum
nanocrystals" (free-download pdf). Science and Technology of Advanced Materials 10: 045004. Bibcode2009STAdM..10d5004S.
doi:10.1088/1468-6996/10/4/045004.
208
209
Periodic table
Valence electron
In chemistry, valence electrons are the electrons of an atom that can
participate in the formation of chemical bonds with other atoms.
Valence electrons are the "own" electrons, present in the free neutral
atom, that combine with valence electrons of other atoms to form
chemical bonds. In a single covalent bond both atoms contribute one
valence electron to form a shared pair. For main group elements, only
the outermost electrons are valence electrons. In transition metals,
some inner-shell electrons are also valence electrons.
Valence electrons are important in determining how the atom reacts
chemically with other atoms. Atoms with a complete (closed) shell of
valence electrons (corresponding to an electron configuration s2p6)
tend to be chemically inert. Atoms with one or two valence electrons
more than a closed shell are highly reactive because the extra electrons
are easily removed to form positive ions. Atoms with one or two
valence electrons fewer than a closed shell are also highly reactive
because of a tendency either to gain the missing electrons and form
negative ions, or to share electrons and form covalent bonds.
Valence electrons have the ability, like electrons in inner shells, to absorb or release energy in the form of photons.
This gain or loss of energy can trigger an electron to move (jump) to another shell or even break free from the atom
and its valence shell. When an electron absorbs energy in the form of one or more photons, then it moves to a more
outer shell depending on the amount of energy gained. (See also : electrons in an excited state). When an electron
loses energy (photons), then it moves to a more inner shell.
Valence electron
210
Valence
electrons
1
See note *
8**
* The general method for counting valence electrons is generally not useful for transition metals. Instead the
modified d electron count method is used.
** Except for helium, which has only two valence electrons.
Valence electron
defined as those outside a noble-gas core.[2] For example, manganese (Mn) has configuration 1s2 2s2 2p6 3s2 3p6 4s2
3d5. This is abbreviated to (Ar) 4s2 3d5, where (Ar) denotes a core configuration identical to that of argon. In this
atom, the 3d electrons have energies similar to those of the 4s electrons, and much higher than for the 3s and 3p
electrons. In effect there are seven valence electrons (4s2 3d5) outside the argon-like core. This is consistent with the
chemical fact that manganese can have oxidation states as high as +7 (in the permanganate ion MnO4-).
Towards the right of each transition metal series, the d electrons descend to lower energies and have less valence
electron character. Thus although nickel has in principle ten valence electrons (4s2 3d8), the oxidation state never
exceeds four. For zinc and succeeding elements, the 3d subshell is complete and the 3d electrons are considered core
electrons.
Since the number of valence electrons which actually participate in chemical reactions is difficult to predict, the
concept of valence electrons is less useful for transition metals than for main group elements. As mentioned above,
the d electron count provides a more useful tool for the understanding of the chemistry of these elements.
211
Valence electron
212
Nonmetallic elements have low electrical conductivity and act as insulators. They are found to the right of the
periodic table with valence shells which are at least half full (except for boron). Their ionization energies are large so
that electrons cannot leave an atom easily when an electric field is applied, and they conduct only very small electric
currents. Examples of solid elemental insulators are diamond (an allotrope of carbon) and sulfur.
Solid compounds containing metals can also be insulators if the valence electrons of the metal atoms are used to
form ionic bonds. For example, although elemental sodium is a metal, solid sodium chloride is an insulator because
the valence electron of sodium is transferred to chlorine to form an ionic bond and cannot move easily in an electric
field.
Semiconductors have an electrical conductivity intermediate between metals and nonmetals, and also differ from
metals in that their conductivity increases with temperature. The typical elemental semiconductors are silicon and
germanium with four valence electrons each. Their properties are best explained using band theory, as a consequence
of a small energy gap between a valence band which contains the valence electrons at absolute zero, and a
conduction band to which valence electrons are excited by thermal energy.
References
[1] Petrucci R.H., Harwood W.S. and Herring F.G., General Chemistry (8th edn, Prentice-Hall 2002), p.339
[2] Miessler G.L. and Tarr, D.A., Inorganic Chemistry (2nd edn. Prentice-Hall 1999). p.48
External links
1. Francis, Eden. Valence Electrons (http://dl.clackamas.cc.or.us/ch104-06/valence_electrons.htm).
Periodic table
The periodic table of the chemical elements (also known as the periodic table or periodic table of the elements)
is a tabular display of the 118 known chemical elements organized by selected properties of their atomic structures.
Elements are presented by increasing atomic number, the number of protons in an atom's atomic nucleus. While
rectangular in general outline, gaps are included in the horizontal rows (known as periods) as needed to keep
elements with similar properties together in vertical columns (known as groups), e.g. alkali metals, alkali earths,
halogens, noble gases.[1]
The following is the periodic table as defined by the International Union of Pure and Applied Chemistry (IUPAC):
Group#
10
11
12
13
14
15
16
17
18
Period
1
1
H
2
He
3
Li
4
Be
5
B
6
C
7
N
8
O
9
F
10
Ne
11
Na
12
Mg
13
Al
14
Si
15
P
16
S
17
Cl
18
Ar
19
K
20
Ca
21
Sc
22
Ti
29 30 31
Cu Zn Ga
32
Ge
33
As
34
Se
35
Br
36
Kr
37
Rb
38
Sr
39
Y
40 41 42 43
Zr Nb Mo Tc
55
Cs
56
Ba
23
V
*
72 73
lanthanides Hf Ta
24 25 26
Cr Mn Fe
74
W
75
Re
27
Co
28
Ni
44
Ru
45
Rh
46 47 48
Pd Ag Cd
49
In
50
Sn
51
Sb
52
Te
53
I
54
Xe
76
Os
77
Ir
78 79 80
Pt Au Hg
81
Tl
82
Pb
83
Bi
84
Po
85
At
86
Rn
Periodic table
213
7
87
Fr
88
Ra
**
actinides
104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Uuq Uup Uuh Uus Uuo
* Lanthanides (Lanthanoids)
57
La
58 59 60 61 62 63
Ce Pr Nd Pm Sm Eu
** Actinides (Actinoids)
89
Ac
90 91
Th Pa
92
U
64 65 66 67
Gd Tb Dy Ho
93 94 95 96 97 98
Np Pu Am Cm Bk Cf
99
Es
68
Er
69
Tm
70
Yb
71
Lu
This common arrangement of the periodic table separates the lanthanides (lanthanoids) and actinides (actinoids) (the
f-block) from other elements. The wide periodic table incorporates the f-block. The extended periodic table adds the
8th and 9th periods, incorporating the f-block and adding the theoretical g-block.
Element categories in the periodic table
Metals
Alkali
metals
Solids
Liquids
Gases
Unknown
Metalloids
Post-transition
metals
Nonmetals
Unknown
chemical
Other
Halogens Noble
properties
nonmetals
gases
Although there were precursors, the current presentation's invention is generally credited to Russian chemist Dmitri
Mendeleev, who developed a version of the now-familiar tabular presentation in 1869 to illustrate recurring
("periodic") trends in the properties of the then-known elements.[2] The layout of the table has been refined and
extended over time, as new elements have been discovered, and new theoretical models have been developed to
explain chemical behavior.[3]
Since the periodic table accurately predicts the abilities of various elements to combine into chemical compounds,
use of the periodic table is now ubiquitous within the academic discipline of chemistry, providing a useful
framework to classify, systematize, and compare many of the many different forms of chemical behavior. The table
has found many applications not only in chemistry and physics, but also in such diverse fields as geology, biology,
materials science, engineering, agriculture, medicine, nutrition, environmental health, and astronomy. Its principles
are especially important in chemical engineering.
One of the strengths of Mendeleev's presentation is that the original version accurately predicted some of the
properties of then-undiscovered elements expected to fill gaps in his arrangement. For example: "eka-aluminium",
expected to have properties intermediate between aluminium and indium, was discovered with said properties in
1875 and named gallium. No gaps remain in the current 118-element periodic table; all elements from hydrogen to
plutonium except technetium, promethium and neptunium exist in the Earth in macroscopic or recurrently produced
trace quantities. The three said exceptions do exist naturally, but only in trace amounts as the result of rare nuclear
processes from decay of heavy elements. Every element through Copernicium, element 112, has been isolated,
characterized, and named, and elements 113 through 118 have been synthesized in laboratories around the world.
While plutonium is now included among the 91 regularly occurring natural elements, and technetium, promethium,
and neptunium also occur naturally in transient trace amounts, these four elements were first identified and
characterized from technologically produced samples. Numerous synthetic radionuclides of various naturally
occurring elements have been produced as well.
Production of additional synthetic elements beyond atomic number 118 is being pursued; whether the next elements
will neatly fill an eighth period or require modifications to the overall patterns of the present periodic table remains
unknown.
Periodic table
Organizing principles
The main value of the periodic table is the ability to predict the chemical properties of an element based on its
location on the table. It should be noted that the properties vary differently when moving vertically along the
columns of the table than when moving horizontally along the rows.[1]
The layout of the periodic table demonstrates recurring ("periodic") chemical properties. Elements are listed in order
of increasing atomic number (i.e., the number of protons in the atomic nucleus). Rows are arranged so that elements
with similar properties fall into the same columns (groups or families). According to quantum mechanical theories of
electron configuration within atoms, each row (period) in the table corresponded to the filling of a quantum shell of
electrons. There are progressively longer periods further down the table, grouping the elements into s-, p-, d- and
f-blocks to reflect their electron configuration.[1]
Atomic number
By definition, each chemical element has a unique atomic number, the number of protons in its nucleus. Different
atoms of many elements have different numbers of neutrons, which differentiates between isotopes of an element.
For example, all atoms of hydrogen have one proton, and no atoms of any other element have exactly one proton. On
the other hand, a hydrogen atom can have one or two neutrons in its nucleus, or none at all, yet all of these cases are
isotopes of hydrogen, not instances of some other element. (A hydrogen atom with no neutrons in addition to its sole
proton is called protium, one with one neutron in addition to its proton is called deuterium, and one with two
additional neutrons, tritium.)
In the modern periodic table, the elements are placed progressively in each row (period) from left to right in the
sequence of their atomic numbers, with each new row starting with the next atomic number following the last
number in the previous row. No gaps or duplications exist. Since the elements can be uniquely sequenced by atomic
number, conventionally from lowest to highest, sets of elements are sometimes specified by such notation as
"through", "beyond", or "from ... through", as in "through iron", "beyond uranium", or "from lanthanum through
lutetium". The terms "light" and "heavy" are sometimes also used informally to indicate relative atomic numbers (not
densities), as in "lighter than carbon" or "heavier than lead", although technically the weight or mass of atoms of an
element (their atomic weights or atomic masses) do not always increase monotonically with their atomic numbers.
214
Periodic table
215
The significance of atomic numbers to the organization of the periodic table was not appreciated until the existence
and properties of protons and neutrons became understood. Mendeleev's periodic tables instead used atomic weights,
information determinable to fair precision in his time, which worked well enough in most cases to give a powerfully
predictive presentation far better than any other comprehensive portrayal of the chemical elements' properties then
possible. Substitution of atomic numbers, once understood, gave a definitive, integer-based sequence for the
elements, still used today even as new synthetic elements are being produced and studied.
G F
D P
Period
1
1s
2s
2p
3s
3p
4s
3d 4p
5s
4d 5p
6s
4f 5d 6p
7s
5f 6d 7p
8s 5g 6f 7d 8p
The total number of electron shells an atom has determines the period to which it belongs. Each shell is divided into
different subshells, which as atomic number increases are filled in roughly this order (the Aufbau principle) (see
table).[5] Hence the structure of the periodic table. Since the outermost electrons determine chemical properties,
those with the same number of valence electrons are generally grouped together.[1]
Progressing through a group from lightest element to heaviest element, the outer-shell electrons (those most readily
accessible for participation in chemical reactions) are all in the same type of orbital, with a similar shape, but with
increasingly higher energy and average distance from the nucleus. For instance, the outer-shell (or "valence")
electrons of the first group, headed by hydrogen, all have one electron in an s orbital. In hydrogen, that s orbital is in
the lowest possible energy state of any atom, the first-shell orbital (and represented by hydrogen's position in the first
period of the table).[6] In francium, the heaviest element of the group, the outer-shell electron is in the seventh-shell
orbital, significantly further out on average from the nucleus than those electrons filling all the shells below it in
energy. As another example, both carbon and lead have four electrons in their outer shell orbitals.[1]
Note that as atomic number (i.e., charge on the atomic nucleus) increases, this leads to greater spin-orbit coupling
between the nucleus and the electrons, reducing the validity of the quantum mechanical orbital approximation model,
which considers each atomic orbital as a separate entity.
Periodic table
Groups
A group or family is a vertical column in the periodic table. Groups are considered the most important method of
classifying the elements. In some groups, the elements have very similar properties and exhibit a clear trend in
properties down the group. Under the international naming system, the groups are numbered numerically 1 through
18 from the left most column (the alkali metals) to the right most column (the noble gases).[7] The older naming
systems differed slightly between Europe and America (the table shown in this section shows the old American
Naming System).[8]
Some of these groups have been given trivial (unsystematic) names, such as the alkali metals, alkaline earth metals,
halogens, pnictogens, chalcogens, and noble gases. However, some other groups, such as group 7, have no trivial
names and are referred to simply by their group numbers, since they display fewer similarities and/or vertical
trends.[7]
Modern quantum mechanical theories of atomic structure explain group trends by proposing that elements within the
same group generally have the same electron configurations in their valence shell, which is the most important factor
in accounting for their similar properties.[1]
Elements in the same group show patterns in atomic radius, ionization energy, and electronegativity. From top to
bottom in a group, the atomic radii of the elements increase. Since there are more filled energy levels, valence
electrons are found farther from the nucleus. From the top, each successive element has a lower ionization energy
because it is easier to remove an electron since the atoms are less tightly bound. Similarly, a group has a top to
bottom decrease in electronegativity due to an increasing distance between valence electrons and the nucleus.[9]
Periods
A period is a horizontal row in the periodic table. Although groups are the most common way of classifying
elements, there are some regions of the periodic table where the horizontal trends and similarities in properties are
more significant than vertical group trends. This can be true in the d-block (or "transition metals"), and especially for
the f-block, where the lanthanides and actinides form two substantial horizontal series of elements.
Elements in the same period show
trends in atomic radius, ionization
energy,
electron
affinity,
and
electronegativity. Moving left to right
across a period, atomic radius usually
decreases. This occurs because each
successive element has an added
proton and electron which causes the
electron to be drawn closer to the
nucleus.[10] This decrease in atomic
radius also causes the ionization
Periodic trend for ionization energy. Each period begins at a minimum for the alkali
energy to increase when moving from
metals, and ends at a maximum for the noble gases.
left to right across a period. The more
tightly bound an element is, the more energy is required to remove an electron. Electronegativity increases in the
same manner as ionization energy because of the pull exerted on the electrons by the nucleus.[9] Electron affinity
also shows a slight trend across a period. Metals (left side of a period) generally have a lower electron affinity than
nonmetals (right side of a period) with the exception of the noble gases.[11]
216
Periodic table
Blocks
Because of the importance of the
outermost electron shell, the different
regions of the periodic table are
sometimes referred to as periodic table
blocks, named according to the
subshell in which the "last" electron
resides. The s-block comprises the first
two groups (alkali metals and alkaline
earth metals) as well as hydrogen and
helium. The p-block comprises the last
six groups which are groups 13
through 18 in IUPAC (3A through 8A
in American) and contains, among
others, all of the semimetals. The
This diagram shows the periodic table blocks with the CAS (American Group Numbering
d-block comprises groups 3 through 12
System).
in IUPAC (or 3B through 8B in
American group numbering) and contains all of the transition metals. The f-block, usually offset below the rest of the
periodic table, comprises the lanthanides and actinides.[12]
Uncertainties after element 118
Element 118 completes the seventh period of the periodic table. Since the properties of any additional elements are
still unknown, it is unclear whether they will continue the pattern of the currently accepted periodic table as an
additional period (Period 8), or require further adaptations or adjustments to the currently known patterns. Glenn T.
Seaborg expected the next 50 elements to form an eighth period, including a two-element s-block for elements 119
and 120, a g-block (the first) for the next 18 elements (121-138), filling a g-shell of electrons, and the 30 additional
elements continuing the current p-, d-, and f-blocks.[13] [14] However, some physicists, including Pekka Pyykk, have
theorized that these additional elements will deviate from the Madelung energy-ordering rule, which predicts how
electron shells are filled, and thus affect the appearance of the present periodic table.[15]
217
Periodic table
218
The periodic table as commonly presented, with horizontal periods, vertical groups, and
highlighting to show similar elements. Rather than being incorporated in their proper
places, the lanthanides and actinides are here shown in separate rows beneath the other
elements, providing a more convenient (and aesthetically more pleasing), but less
accurate, layout.
Periodic table
Hydrogen is usually placed above lithium, although its chemistry differs substantially from that of lithium and the
other alkali metals; some periodic tables place it on its own.[1]
Elements with atomic numbers greater than 82, as well as technetium and promethium, have no stable isotopes; the
atomic mass of each of these element's isotope having the longest half-life is typically reported on periodic tables
with parentheses.[18]
History
In 1789, Antoine Lavoisier published a list
of 33 chemical elements. Although Lavoisier
grouped the elements into gases, metals,
non-metals, and earths, chemists spent the
following century searching for a more
precise classification scheme. In 1829,
Johann Wolfgang Dbereiner observed that
many of the elements could be grouped into
triads (groups of three) based on their
chemical properties. Lithium, sodium, and
potassium, for example, were grouped
together as being soft, reactive metals.
Dbereiner also observed that, when
arranged by atomic weight, the second
member of each triad was roughly the
average of the first and the third.[19] This
became known as the Law of Triads.[20]
German chemist Leopold Gmelin worked
with this system, and by 1843 he had
identified ten triads, three groups of four,
and one group of five. Jean Baptiste Dumas
published work in 1857 describing
relationships between various groups of
Mendeleev's 1869 periodic table; note that his arrangement presents the periods
metals. Although various chemists were able
vertically, and the groups horizontally
to identify relationships between small
groups of elements, they had yet to build one scheme that encompassed them all.[19]
German chemist August Kekul had observed in 1858 that carbon has a tendency to bond with other elements in a
ratio of one to four. Methane, for example, has one carbon atom and four hydrogen atoms. This concept eventually
became known as valency. In 1864, fellow German chemist Julius Lothar Meyer published a table of the 49 known
elements arranged by valency. The table revealed that elements with similar properties often shared the same
valency.[21]
English chemist John Newlands produced a series of papers in 1864 and 1865 that described his own classification
of the elements: he noted that when listed in order of increasing atomic weight, similar physical and chemical
properties recurred at intervals of eight, which he likened to the octaves of music.[22] [23] This Law of Octaves,
however, was ridiculed by his contemporaries, and the Chemical Society refused to publish his work.[24]
Nonetheless, Newlands was able to draft an atomic table and use it to predict the existence of missing elements, such
as germanium. The Chemical Society only acknowledged the significance of his discoveries some five years after
they credited Mendeleev.
219
Periodic table
References
[1] Gray, Theodore (2009). The Elements: A Visual Exploration of Every Known Atom in the Universe. New York: Black Dog & Leventhal
Publishers. p.240. ISBN978-1-57912-814-2.
[2] Dimitri Mendelejew: ber die Beziehungen der Eigenschaften zu den Atomgewichten der Elemente. In: Zeitschrift fr Chemie. 1869, pp.
405406.
[3] http:/ / www. iupac. org/ didac/ Didac%20Eng/ Didac01/ Content/ S01. htm
[4] Koppenol, W. H. (2002). "Naming of New Elements (IUPAC Recommendations 2002)" (http:/ / media. iupac. org/ publications/ pac/ 2002/
pdf/ 7405x0787. pdf) (PDF). Pure and Applied Chemistry 74 (5): 787791. doi:10.1351/pac200274050787. .
[5] Moore, p. 46
[6] Hornback, Joseph (2006). Organic Chemistry (2nd ed.). Pacific Grove: Thomson Brooks/Cole. p.62. ISBN978-0-534-49317-2.
OCLC66441248.
[7] Leigh, G. J. Nomenclature of Inorganic Chemistry: Recommendations 1990. Blackwell Science, 1990. ISBN 0632024941.
[8] Leigh, Jeffery. "Periodic Tables and IUPAC" (http:/ / www. iupac. org/ publications/ ci/ 2009/ 3101/ 1_leigh. html). Chemistry International:
The News Magazine of The International Union of Pure and Applied Chemistry (IUPAC). . Retrieved 23 March 2011.
[9] Moore, p. 111
[10] Mascetta, Joseph (2003). Chemistry The Easy Way (4th ed.). New York: Hauppauge. p.50. ISBN9780764119781. OCLC52047235.
[11] Kotz, John; Treichel, Paul; Townsend, John (2009). Chemistry and Chemical Reactivity, Volume 2 (7th ed.). Belmont: Thomson
Brooks/Cole. p.324. ISBN9780495387121. OCLC220756597.
[12] Jones, Chris (2002). d- and f-block chemistry. New York: J. Wiley & Sons. p.2. ISBN9780471224761. OCLC300468713.
220
Periodic table
[13] Seaborg, Glenn (August 26, 1996). "An Early History of LBNL" (http:/ / www. lbl. gov/ LBL-PID/ Nobelists/ Seaborg/ 65th-anniv/ 29.
html). .
[14] Frazier, K. (1978). "Superheavy Elements". Science News 113 (15): 236238. doi:10.2307/3963006. JSTOR3963006.
[15] "Extended elements: new periodic table" (http:/ / www. rsc. org/ Publishing/ ChemScience/ Volume/ 2010/ 11/ Extended_elements. asp).
2010. .
[16] An example (among many) showing several of these descriptors: Painless Learning Placemats: Periodic Table of the Elements. M. Ruskin
Co.. 2000. p.2.
[17] Science Standards of Learning Curriculum Framework (http:/ / www. doe. virginia. gov/ VDOE/ Instruction/ Science/ ScienceCF-PS. doc)
[18] "Dynamic periodic table" (http:/ / www. ptable. com/ ). Ptable.com. 2011-10-06. . Retrieved 2011-10-30.
[19] Ball, p. 100
[20] Horvitz, Leslie (2002). Eureka!: Scientific Breakthroughs That Changed The World. New York: John Wiley. p.43. ISBN9780471233411.
OCLC50766822.
[21] Ball, p. 101
[22] Newlands, John A. R. (1864-08-20). "On Relations Among the Equivalents" (http:/ / web. lemoyne. edu/ ~giunta/ EA/ NEWLANDSann.
HTML#newlands3). Chemical News 10: 9495. .
[23] Newlands, John A. R. (1865-08-18). "On the Law of Octaves" (http:/ / web. lemoyne. edu/ ~giunta/ EA/ NEWLANDSann.
HTML#newlands4). Chemical News 12: 83. .
[24] Bryson, Bill (2004). A Short History of Nearly Everything. London: Black Swan. pp.141142. ISBN9780552151740.
[25] Ball, pp. 100102
[26] Pullman, Bernard (1998). The Atom in the History of Human Thought. Translated by Axel Reisinger. Oxford University Press. p.227.
ISBN0-19-515040-6.
[27] Ball, p. 105
[28] Atkins, P. W. (1995). The Periodic Kingdom. HarperCollins Publishers, Inc.. p.87. ISBN0-465-07265-8.
[29] Ball, p. 111
[30] Adloff, Jean-Pierre; Kaufman, George B. (2005-09-25). Francium (Atomic Number 87), the Last Discovered Natural Element (http:/ /
chemeducator. org/ sbibs/ s0010005/ spapers/ 1050387gk. htm). The Chemical Educator 10 (5). Retrieved on 2007-03-26.
[31] Hoffman, D. C.; Lawrence, F. O.; Mewherter, J. L.; Rourke, F. M. (1971). "Detection of Plutonium-244 in Nature" (http:/ / www. nature.
com/ nature/ journal/ v234/ n5325/ abs/ 234132a0. html). Nature 234 (5325): 132134. Bibcode1971Natur.234..132H.
doi:10.1038/234132a0. .
[32] Ball, p. 123
[33] Barber, Robert C.; Gggeler, Heinz W.; Karol, Paul J.; Nakahara, Hiromichi; Vardaci, Emanuele; Vogt, Erich (2009). "[IUPAC]Element
112 is Named Copernicium" (http:/ / www. iupac. org/ web/ nt/ 2010-02-20_112_Copernicium). Pure and Applied Chemistry (iupac.org) 81
(7): 1331. doi:10.1351/PAC-REP-08-03-05. . Retrieved 2010-06-12.
[34] Barber, Robert C.; Karol, Paul J; Nakahara, Hiromichi; Vardaci, Emanuele; Vogt, Erich W. (2011). "Discovery of the elements with atomic
numbers greater than or equal to 113 (IUPAC Technical Report)". Pure Appl. Chem. 83 (7): 1485. doi:10.1351/PAC-REP-10-05-01.
Bibliography
Ball, Philip (2002). The Ingredients: A Guided Tour of the Elements. Oxford University Press.
ISBN0-19-284100-9.
Bouma, J. (1989). "An Application-Oriented Periodic Table of the Elements". J. Chem. Ed. 66 (9): 741.
Bibcode1989JChEd..66..741B. doi:10.1021/ed066p741.
Hjrland, Birger (2011). "The periodic table and the philosophy of classification" (http://ucla.academia.edu/
EricScerri/Papers/432740/Forum_The_Philosophy_of_Classification). Knowledge Organization 38 (1): 921.
Retrieved 2011-03-13.
Kean, Sam (2010). The Disappearing Spoon - and other true tales from the Periodic Table. London: Black Swan.
ISBN978-0-552-77750-6.
Levi, Primo (1984). The Periodic Table [1975]. London: Penguin Books. ISBN978-0-141-39944-7.
Mazurs, E.G (1974). Graphical Representations of the Periodic System During One Hundred Years. Alabama:
University of Alabama Press.
Moore, John (2003). Chemistry For Dummies. New York: Wiley Publications. p.111. ISBN978-0-7645-5430-8.
OCLC51168057.
Scerri, Eric (2007). The periodic table: its story and its significance. Oxford: Oxford University Press.
ISBN0-19-530573-6.
221
Periodic table
External links
Periodic trends
In chemistry, periodic trends are the tendencies of certain elemental
characteristics to increase or decrease as one progresses along a row or
column of the periodic table of elements.
Atomic radius
The atomic radius is the distance from the atomic nucleus to the
The Periodic Trends
outermost stable electron orbital in an atom that is at equilibrium. The
atomic radius tends to decrease as one progresses across a period from
left to right because the effective nuclear charge increases, thereby attracting the orbiting electrons and lessening the
radius. The atomic radius usually increases while going down a group due to the addition of a new energy level
(shell). However, diagonally, the number of protons has a larger effect than the sizeable radius. For example, lithium
(145 picometer) has a smaller atomic radius than magnesium (150 picometer). Atomic radius decreases from left to
right across a period, and also increases from top to bottom down a group.
Ionization potential
The ionization potential (or the ionization energy) is the minimum amount of energy required to remove one electron
from each atom in a mole of atoms in the gaseous state. The first ionization energy is the energy required to remove
one, the nth ionization energy is the energy required to remove the atom's nth electron, after the (n1) electrons
before it have been removed. Trend-wise, ionization potentials tend to increase while one progresses across a period
because the greater number of protons (higher nuclear charge) attract the orbiting electrons more strongly, thereby
increasing the energy required to remove one of the electrons.
As one progresses down a group on the periodic table, the ionization energy will likely decrease, since the valence
electrons are farther away from the nucleus and experience a weaker; attraction to the nucleus's positive charge.
There will be an increase of ionization energy from left to right of a given period and a decrease from top to bottom.
As a rule, it requires far less energy to remove an outer-shell electron than an inner-shell electron. As a result the
ionization energies for a given element will increase steadily within a given shell, and when starting on the next shell
down will show a drastic jump in ionization energy. Simply put, the lower the principal quantum number, the higher
the ionization energy for the electrons within that shell. The exceptions are the elements in the boron and oxygen
family which require slightly less energy than the general trend.
222
Periodic trends
Electron affinity
The electron affinity of an atom can be described either as the energy gained by an atom when an electron is added to
it, or conversely as the energy required to detach an electron from a singly charged anion. The sign of the electron
affinity can be quite confusing, as atoms that become more stable with the addition of an electron (and so are
considered to have a higher electron affinity) show a decrease in potential energy; i.e. the energy gained by the atom
appears to be negative. For atoms that become less stable upon gaining an electron, potential energy increases, which
implies that the atom gains energy. In such a case, the atom's electron affinity value is positive.[1] Consequently,
atoms with a more negative electron affinity value are considered to have a lower electron affinity (they are more
receptive to gaining electrons), and vice versa. However in the reverse scenario where electron affinity is defined as
the energy required to detach an electron from an anion, the energy value obtained will be of the same magnitude but
have the opposite sign. This is because those atoms with a high electron affinity are less inclined to give up an
electron, and so take more energy to remove the electron from the atom. In this case, the atom with the more positive
energy value has the higher electron affinity. As one progresses from left to right across a period, the electron
affinity will increase.
Electronegativity
Electronegativity is a measure of the ability of an atom or molecule to attract pairs of electrons in the context of a
chemical bond. The type of bond formed is largely determined by the difference in electronegativity between the
atoms involved, using the Pauling scale. Trend-wise, as one moves from left to right across a period in the periodic
table, the electronegativity increases due to the stronger attraction that the atoms obtain as the nuclear charge
increases. Moving down a group, the electronegativity decreases due to the longer distance between the nucleus and
the valence electron shell, thereby decreasing the attraction, making the atom have less of an attraction for electrons
or protons.
In the group 13 elements electronegativity increases from Aluminium to Thallium. In group 14 electronegativity of
Lead is higher than that of Tin.
Metallic Properties
Metallic property decreases across a period with increase in number of valence electrons as well as a decrease in
atomic radius, and it increases down the group with increase in number of shells and atomic radius.
Non-metallic properties
Non-metallic property increases across a period and decreases down the group due to the same reason.
References
[1] http:/ / www. sparknotes. com/ chemistry/ fundamentals/ atomicstructure/ section3. rhtml
http://www.jstage.jst.go.jp/article/jlve/33/2/33_67/_article
223
Period
224
Period
In the periodic table of the elements, elements are arranged in a series of rows (or periods) so that those with similar
properties appear in vertical columns. Elements of the same period have the same number of electron shells; with
each group across a period, the elements have one more proton and electron and become less metallic. This
arrangement reflects the periodic recurrence of similar properties as the atomic number increases. For example, the
alkaline metals lie in one group (group 1) and share similar properties, such as high reactivity and the tendency to
lose one electron to arrive at a noble-gas electronic configuration. The periodic table of elements has a total of 118
elements.
Modern quantum mechanics explains
these periodic trends in properties in
terms of electron shells. As atomic
number increases, shells fill with
electrons in approximately the order
shown at right. The filling of each shell
corresponds to a row in the table.
In the s-block and p-block of the
periodic table, elements within the
same period generally do not exhibit
trends and similarities in properties
(vertical trends down groups are more
significant). However in the d-block,
trends
across
periods
become
significant, and in the f-block elements
show a high degree of similarity across
periods (particularly the lanthanides).
Periods
Seven periods of elements occur
naturally on Earth. For period 8, which
includes elements which may be
synthesized after 2011, see the extended periodic table.
A group in chemistry means a family of objects with similarities like different families.
1
H
2
He
The first period contains fewer elements than any other, with only two, hydrogen and helium. They therefore do not
follow the octet rule. Chemically, helium behaves as a noble gas, and thus is taken to be part of the group 18
elements. However, in terms of its nuclear structure it belongs to the s block, and is therefore sometimes classified as
a group 2 element, or simultaneously both 2 and 18. Hydrogen readily loses and gains an electron, and so behaves
chemically as both a group 1 and a group 17 element.
Period
225
Hydrogen (H) is the most abundant of the chemical elements, constituting roughly 75% of the universe's
elemental mass.[1] Ionized hydrogen is just a proton. Stars in the main sequence are mainly composed of
hydrogen in its plasma state. Elemental hydrogen is relatively rare on Earth, and is industrially produced from
hydrocarbons such as methane. Hydrogen can form compounds with most elements and is present in water and
most organic compounds.[2]
Helium (He) exists only as a gas except in extreme conditions.[3] It is the second lightest element and is the
second most abundant in the universe.[4] Most helium was formed during the Big Bang, but new helium is created
through nuclear fusion of hydrogen in stars.[5] On Earth, helium is relatively rare, only occurring as a byproduct
of the natural decay of some radioactive elements.[6] Such 'radiogenic' helium is trapped within natural gas in
concentrations of up to seven percent by volume.[7]
13 14 15 16 17 18
#
3 4 5
Name Li Be B
6
C
7
N
8
O
9 10
F Ne
Period 2 elements involve the 2s and 2p orbitals. They include the biologically most essential elements besides
hydrogen: carbon, nitrogen, and oxygen.
Lithium (Li) is the lightest metal and the least dense solid element.[8] In its non-ionized state it is one of the most
reactive elements, and so is only ever found naturally in compounds. It is the heaviest primordial element forged
in large quantities during the Big Bang.
Beryllium (Be) has one of the highest melting points of all the light metals. Small amounts of beryllium were
synthesised during the Big Bang, although most of it decayed or reacted further within stars to create larger
nucleii, like carbon, nitrogen or oxygen. Beryllium is classified by the International Agency for Research on
Cancer as Group 1 carcinogens.[9] Between 1% and 15% of people are sensitive to beryllium and may develop an
inflammatory reaction in their respiratory system and skin, called chronic beryllium disease.[10]
Boron (B) does not occur naturally as a free element, but in compounds such as borates. It is an essential plant
micronutrient, required for cell wall strength and development, cell division, seed and fruit development, sugar
transport and hormone development,[11] [12] though high levels are toxic.
Carbon (C) is the fourth most abundant element in the universe by mass after hydrogen, helium and oxygen[13]
and is the second most abundant element in the human body by mass after oxygen,[14] the third most abundant by
number of atoms.[15] There are an almost infinite number of compounds that contain carbon due to carbon's
ability to form long stable chains of CC bonds.[16] [17] All organic compounds, those essential for life, contain
at least one atom of carbon;[16] [17] combined with hydrogen, oxygen, nitrogen, sulfur, and phosphorus, carbon is
the basis of every important biological compound.[17]
Nitrogen (N) is found mainly as mostly inert diatomic gas, N2, which makes up 78% of the Earth's atmosphere. It
is an essential component of proteins and therefore of life.
Oxygen (O) comprising 21% of the atmosphere and is required for respiration by all (or nearly all) animals, as
well as being the principal component of water. Oxygen is the third most abundant element in the universe, and
oxygen compounds dominate the Earth's crust.
Fluorine (F) is the most reactive element in its non-ionized state, and so is never found that way in nature.
Neon (Ne) is a noble gas used in neon lighting.
Period
226
13 14 15 16 17 18
#
11 12 13 14 15 16 17 18
Name Na Mg Al Si P S Cl Ar
All period three elements occur in nature and have at least one stable isotope. All but the noble gas argon are all
essential to basic geology and biology.
Sodium (Na) is an alkali metal. It is present in Earth's oceans in large quantities in the form of sodium chloride
(table salt).
Magnesium (Mg) is an alkaline earth metal. Magnesium ions are found in chlorophyll.
Aluminium (Al) is a poor metal. It is the most abundant metal in the Earth's crust.
Silicon (Si) is a metalloid. It is a semiconductor, making it the principal component in many integrated circuits.
Silicon dioxide is the principal constituent of sand.
Phosphorus (P) is a nonmetal essential to DNA. It is highly reactive, and as such is never found in nature as a free
element.
Sulfur (S) is a nonmetal. It is found in two amino acids: cysteine and methionine.
Chlorine (Cl) is a halogen. It is used as a disinfectant, especially in swimming pools.
Argon (Ar) is a noble gas, making it almost entirely nonreactive. Incandescent lamps are often filled with noble
gases such as argon in order to preserve the filaments at high temperatures.
Atomic
number
Name
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
10 11 12 13 14 15 16 17 18
Period
227
10 11 12 13 14 15 16 17 18
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Period 5 contains the heaviest few elements that have biological roles, molybdenum and iodine. (Tungsten, a period
6 element, is the only heavier element that has a biological role.) It includes technetium, the lightest exclusively
radioactive element.
3 (Lanthanides)
9 10 11 12 13 14 15 16 17 18
#
55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Name Cs Ba La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Period 6 is the first period to include the f-block, with the lanthanides (also known as the rare earth elements), and
includes the heaviest stable elements. Many of these heavy metals are toxic and some are radioactive, but platinum
and gold are largely inert.
3 (Actinides)
9 10 11 12 13
14
15
16
17
18
#
87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Name Fr Ra Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Uuq Uup Uuh Uus Uuo
All elements of period 7 are radioactive. This period contains the heaviest element which occurs naturally on earth,
uranium. All of the subsequent elements in the period have been synthesized artificially. Whilst some of these (e.g.
plutonium) are now available in tonne quantities, most are extremely rare, having only been prepared in microgram
amounts or less. Some of the later elements have only ever been identified in laboratories in quantities of a few
atoms at a time.
Although the rarity of many of these elements means that experimental results are not very extensive, periodic and
group trends in behaviour appear to be less well defined for period 7 than for other periods. Whilst francium and
radium do show typical properties of Groups 1 and 2 respectively, the actinides display a much greater variety of
behaviour and oxidation states than the lanthanides. Initial studies suggest Group 14 element ununquadium appears
to be a noble gas instead of a poor metal, and group 18 element ununoctium probably is not a noble gas.[18] These
peculiarities of period 7 may be due to a variety of factors, including a large degree of spin-orbit coupling and
relativistic effects, ultimately caused by the very high positive electrical charge from their massive atomic nuclei.
Period
228
Alkaline
earth
metals
Metalloids
Transition
metals
Post-transition
metals
Nonmetals
Unknown
chemical
Other
Halogens Noble
properties
nonmetals
gases
References
[1] Palmer, David (November 13, 1997). "Hydrogen in the Universe" (http:/ / imagine. gsfc. nasa. gov/ docs/ ask_astro/ answers/ 971113i. html).
NASA. . Retrieved 2008-02-05.
[2] "hydrogen". Encyclopdia Britannica. 2008.
[3] "Helium: physical properties" (http:/ / www. webelements. com/ helium/ physics. html). WebElements. . Retrieved 2008-07-15.
[4] "Helium: geological information" (http:/ / www. webelements. com/ helium/ geology. html). WebElements. . Retrieved 2008-07-15.
[5] Cox, Tony (1990-02-03). "Origin of the chemical elements" (http:/ / www. newscientist. com/ article/ mg12517027.
000-origin-of-the-chemical-elements. html). New Scientist. . Retrieved 2008-07-15.
[6] "Helium supply deflated: production shortages mean some industries and partygoers must squeak by.". Houston Chronicle. 2006-11-05.
[7] Brown, David (2008-02-02). "Helium a New Target in New Mexico" (http:/ / www. aapg. org/ explorer/ 2008/ 02feb/ helium. cfm). American
Association of Petroleum Geologists. . Retrieved 2008-07-15.
[8] Lithium (http:/ / www. webelements. com/ lithium/ ) at WebElements.
[9] "IARC Monograph, Volume 58" (http:/ / www. inchem. org/ documents/ iarc/ vol58/ mono58-1. html). International Agency for Research on
Cancer. 1993. . Retrieved 2008-09-18.
[10] Information (http:/ / www. chronicberylliumdisease. com/ medical/ med_bediseases. htm#cbd) about chronic beryllium disease.
[11] "Functions of Boron in Plant Nutrition" (http:/ / www. borax. com/ agriculture/ files/ an203. pdf) (PDF). U.S. Borax Inc.. .
[12] Blevins, Dale G.; Lukaszewski, Krystyna M. (1998). "Functions of Boron in Plant Nutrition". Annual Review of Plant Physiology and Plant
Molecular Biology 49: 481500. doi:10.1146/annurev.arplant.49.1.481. PMID15012243.
[13] Ten most abundant elements in the universe, taken from The Top 10 of Everything, 2006, Russell Ash, page 10. Retrieved October 15, 2008.
(http:/ / plymouthlibrary. org/ faqelements. htm)
[14] Chang, Raymond (2007). Chemistry, Ninth Edition. McGraw-Hill. pp.52. ISBN0-07-110595-6.
[15] Freitas Jr., Robert A. (1999). Nanomedicine (http:/ / www. foresight. org/ Nanomedicine/ Ch03_1. html). Landes Bioscience. Tables 3-1 &
3-2. ISBN1570596808. .
[16] "Structure and Nomenclature of Hydrocarbons" (http:/ / chemed. chem. purdue. edu/ genchem/ topicreview/ bp/ 1organic/ organic. html).
Purdue University. . Retrieved 2008-03-23.
[17] Alberts, Bruce; Alexander Johnson, Julian Lewis, Martin Raff, Keith Roberts, Peter Walter. Molecular Biology of the Cell (http:/ / www.
ncbi. nlm. nih. gov/ books/ bv. fcgi?highlight=carbon& rid=mboc4. section. 165). Garland Science. .
[18] See references in the articles Ununquadium, Ununoctium
Group
Group
In chemistry, a group (also known as a
family) is a vertical column in the
periodic table of the chemical
elements. There are 18 groups in the
standard periodic table, including the
d-block elements, but excluding the
f-block elements.
The modern explanation of the pattern
of the table is that the elements in a
group have similar configurations of
the outermost electron shells of their
atoms (i.e. the same core charge), as
The periodic table of the chemical elements. The columns represent the groups
most
chemical
properties
are
dominated by the orbital location of the outermost electron. There are three conventional ways of numbering: One
using Arabic numerals, and two using Roman numerals. The Roman numeral names are the original traditional
names of the groups; the Arabic numeral names are those recommended by the International Union of Pure and
Applied Chemistry (IUPAC) to replace the old names in an attempt to reduce the confusion generated by the two
older, but mutually confusing, schemes.
There is considerable confusion surrounding the two old systems in use (old IUPAC and CAS) that combined the use
of Roman numerals with letters. Both systems agree on the Roman numerals, which indicate (approximately) the
highest oxidation number of the elements in that group (and therefore indicates similar chemistry with other
elements with the same Roman numeral), which proceeds in a linearly increasing fashion for the most part, once on
the left of the table, and once on the right (see List of oxidation states of the elements), with some irregularities in the
transition metals. However, the two systems use the letters differently.
In the old IUPAC system the letters A and B were designated to the left (A) and right (B) part of the table, while in
the CAS system the letters A and B were designated to main group elements (A) and transition elements (B). The old
IUPAC system was frequently used in Europe while the CAS was most common in America. The new IUPAC
scheme was developed to replace both systems as they confusingly used the same names to mean different things.
The new system simply numbers the groups increasingly from left to right on the standard periodic table. The
IUPAC proposal was first circulated in 1985 for public comments,[1] and was later included as part of the 1990
edition of the Nomenclature of Inorganic Chemistry.[2]
Groups
The periodic table groups are as follows:
229
Group
230
New IUPAC
numbering
Old IUPAC
(European)
CAS (American)
Name
Group 1
IA
IA
Group 2
IIA
IIA
Group 3
IIIA
IIIB
the scandium family (consisting of the rare earth elements plus the
actinides)
Group 4
IVA
IVB
Group 5
VA
VB
Group 6
VIA
VIB
Group 7
VIIA
VIIB
Group 8
VIII
VIIIB
Group 9
VIII
VIIIB
Group 10
VIII
VIIIB
Group 11
IB
IB
Group 12
IIB
IIB
Group 13
IIIB
IIIA
Group 14
IVB
IVA
Group 15
VB
VA
Group 16
VIB
VIA
Group 17
VIIB
VIIA
Group 18
Group 0
VIIIA
References
Footnotes
[1] Fluck, E. New notations in the periodic table. Pure & App. Chem. 1988, 60, 431-436. (http:/ / www. iupac. org/ publications/ pac/ 1988/ pdf/
6003x0431. pdf)
[2] Leigh, G. J. Nomenclature of Inorganic Chemistry: Recommendations 1990. Blackwell Science, 1990. ISBN 0632024941.
Background
Scerri, E. R. The Periodic Table, Its Story and Its Significance, Oxford University Press, 2007. ISBN
978-0-19-530573-9.
231
Chemical concepts
Ionic radius
Ionic radius, rion, is the radius of an atom's ion. Although neither atoms nor ions have sharp boundaries, it is
important to treat them as if they are hard spheres with radii such that the sum of ionic radii of the cation and anion
gives the distance between the ions in a crystal lattice. Ionic radii are typically given in units of either picometers
(pm) or Angstroms (), with 1= 100pm. Typical values range from 30pm (0.3) to over 200pm (2).
AgX
464
492
Cl
564
555
Br
598
577
Unit cell parameters (in pm, equal to two MX bond lengths) for sodium and silver halides. All compounds crystallize in the NaCl structure.
Ionic radius
232
basis of the fluorides, one would say that Ag+ is larger than Na+, but on the basis of the chlorides and bromides the
opposite appears to be true.[1] This is because the greater covalent character of the bonds in AgCl and AgBr reduces
the bond length and hence the apparent ionic radius of Ag+, an effect which is not present in the halides of the more
electropositive sodium, nor in silver fluoride in which the fluoride ion is relatively unpolarizable.
Pauling used effective nuclear charge to proportion the distance between ions into anionic and a cationic radii.[5] His
data gives the O2- ion a radius of 140 pm.
A major review of crystallographic data led to the publication of revised ionic radii by Shannon.[6] Shannon gives
different radii for different coordination numbers, and for high and low spin states of the ions. To be consistent with
Pauling's radii, Shannon has used a value of rion(O2)= 140pm; data using that value are referred to as "effective"
ionic radii. However, Shannon also includes data based on rion(O2)= 126pm; data using that value are referred to
as "Crystal" ionic radii. Shannon states that "it is felt that crystal radii correspond more closely to the physical size of
ions in a solid."[6] The two sets of data are listed in the two tables below.
Ionic radius
233
Crystal ionic radii in pm of elements in function of ionic charge and spin (ls = low spin, hs=
high spin).
Ions are 6-coordinate unless indicated differently in parentheses (e.g. 146 (4) for
4-coordinate N3).[6]
Number
Name
Symbol
1+
2+
3+
4+
5+
6+
7+
Lithium
Li
90
Beryllium
Be
Boron
Carbon
Nitrogen
Oxygen
Fluorine
11
Sodium
Na
12
Magnesium
Mg
13
Aluminum
Al
14
Silicon
Si
15
Phosphorus
16
Sulfur
17
Chlorine
Cl
19
Potassium
20
Calcium
Ca
21
Scandium
Sc
22
Titanium
Ti
100
81
74.5
23
Vanadium
93
78
72
68
24
Chromium ls
Cr
87
75.5
69
63
58
24
Chromium hs
Cr
94
25
Manganese ls
Mn
81
72
67
47 (4)
39.5 (4) 60
25
Manganese hs
Mn
97
78.5
26
Iron ls
Fe
75
69
26
Iron hs
Fe
92
78.5
27
Cobalt ls
Co
79
68.5
27
Cobalt hs
Co
88.5
75
67
28
Nickel ls
Ni
83
70
62 ls
28
Nickel hs
Ni
29
Copper
Cu
30
Zinc
Zn
31
Gallium
Ga
32
Germanium
Ge
33
Arsenic
As
59
41
30
132 (4)
30
27
126
119
22
116
86
67.5
54
58
170
52
51
167
43
26 (3py)
41
152
114
88.5
72.5
39 (4)
74
91
87
68 ls
88
76
87
67
72
60
8+
Ionic radius
234
34
Selenium
Se
184
64
35
Bromine
Br
37
Rubidium
Rb
38
Strontium
Sr
39
Yttrium
40
Zirconium
Zr
41
Niobium
Nb
86
82
78
42
Molybdenum
Mo
83
79
75
43
Technetium
Tc
44
Ruthenium
Ru
45
Rhodium
Rh
46
Palladium
Pd
47
Silver
Ag
48
Cadmium
Cd
49
Indium
In
50
Tin
Sn
51
Antimony
Sb
52
Tellurium
Te
53
Iodine
54
Xenon
Xe
55
Caesium
Cs
56
Barium
Ba
57
Lanthanum
La
117.2
58
Cerium
Ce
115
101
59
Praseodymium Pr
113
99
60
Neodymium
Nd
61
Promethium
Pm
62
Samarium
Sm
63
Europium
Eu
131
64
Gadolinium
Gd
107.5
65
Terbium
Tb
106.3
66
Dysprosium
Dy
67
Holmium
Ho
104.1
68
Erbium
Er
103
69
Thulium
Tm
117
102
70
Ytterbium
Yb
116
100.8
71
Lutetium
Lu
72
Hafnium
Hf
73
Tantalum
Ta
182
73 (4sq)
56
45 (3py)
53
166
132
104
86
73
78.5 74
70
82
76
70.5
52 (4) 50 (4)
80.5
74
69
73 (2) 100
90
75.5
129
89
108
109
94
83
90
207
76
111
206
70
109
67
62
181
149
121
108.7
90
105.2
100.1
85
86
82
78
Ionic radius
235
74
Tungsten
80
76
74
75
Rhenium
Re
77
72
69
67
76
Osmium
Os
77
71.5
68.5
66.5
77
Iridium
Ir
78
Platinum
Pt
79
Gold
Au
151
80
Mercury
Hg
133
81
Thallium
Tl
164
82
Lead
Pb
83
Bismuth
Bi
84
Polonium
Po
85
Astatine
At
87
Francium
Fr
88
Radium
Ra
89
Actinium
Ac
90
Thorium
Th
91
Protactinium
Pa
116
104
92
92
Uranium
116.5
103
90
87
93
Neptunium
Np
115
101
89
86
94
Plutonium
Pu
114
100
88
85
95
Americium
Am
96
Curium
Cm
111
99
97
Berkelium
Bk
110
97
98
Californium
Cf
109
96.1
82
94
53 (4)
76.5 71
76.5 71
99
71
116
102.5
133
91.5
117
90
108
81
76
194
162 (8)
126
108
124
85
99
Effective ionic radii in pm of elements in function of ionic charge and spin (ls = low spin,
hs= high spin).
Ions are 6-coordinate unless indicated differently in parentheses (e.g. 146 (4) for
4-coordinate N3).[6]
Number
Name
Symbol
Lithium
Li
Beryllium
Be
Boron
Carbon
Nitrogen
Oxygen
Fluorine
11
Sodium
Na
12
Magnesium
Mg
1+
2+
3+
4+
5+
6+
7+
76
45
27
16
146 (4)
16
13
140
133
8
102
72
8+
Ionic radius
236
13
Aluminum
Al
53.5
14
Silicon
Si
15
Phosphorus
16
Sulfur
17
Chlorine
Cl
19
Potassium
20
Calcium
Ca
21
Scandium
Sc
22
Titanium
Ti
86
67
60.5
23
Vanadium
79
64
58
54
24
Chromium ls
Cr
73
61.5
55
49
44
24
Chromium hs
Cr
80
25
Manganese ls
Mn
67
58
53
33 (4)
25.5 (4) 46
25
Manganese hs
Mn
83
64.5
26
Iron ls
Fe
61
55
26
Iron hs
Fe
78
64.5
27
Cobalt ls
Co
65
54.5
27
Cobalt hs
Co
74.5
61
53 hs
28
Nickel ls
Ni
69
56
48 ls
28
Nickel hs
Ni
29
Copper
Cu
30
Zinc
Zn
31
Gallium
Ga
32
Germanium
Ge
33
Arsenic
As
34
Selenium
Se
35
Bromine
Br
37
Rubidium
Rb
38
Strontium
Sr
39
Yttrium
40
Zirconium
Zr
41
Niobium
Nb
72
68
64
42
Molybdenum
Mo
69
65
61
43
Technetium
Tc
64.5
60
56
44
Ruthenium
Ru
68
62
56.5
38 (4) 36 (4)
45
Rhodium
Rh
66.5
60
55
46
Palladium
Pd
59 (2) 86
76
61.5
47
Silver
Ag
115
75
48
Cadmium
Cd
40
44
184
38
37
181
29
12 (3py)
27
138
100
74.5
58.5
25 (4)
60
77
73
54 ls
74
62
73
53
58
198
46
50
196
59 (4sq)
42
31 (3py)
39
152
118
90
72
94
95
59
Ionic radius
237
49
Indium
In
80
50
Tin
Sn
51
Antimony
Sb
52
Tellurium
Te
53
Iodine
54
Xenon
Xe
55
Caesium
Cs
56
Barium
Ba
57
Lanthanum
La
103.2
58
Cerium
Ce
101
87
59
Praseodymium Pr
99
85
60
Neodymium
Nd
61
Promethium
Pm
62
Samarium
Sm
63
Europium
Eu
117
64
Gadolinium
Gd
93.5
65
Terbium
Tb
92.3
66
Dysprosium
Dy
67
Holmium
Ho
90.1
68
Erbium
Er
89
69
Thulium
Tm
103
88
70
Ytterbium
Yb
102
86.8
71
Lutetium
Lu
72
Hafnium
Hf
73
Tantalum
Ta
74
Tungsten
75
69
76
221
60
97
220
56
95
53
48
167
135
107
94.7
76
91.2
86.1
71
72
68
64
66
62
60
Rhenium
Re
63
58
55
53
76
Osmium
Os
63
57.5
54.5
52.5
77
Iridium
Ir
62.5
57
78
Platinum
Pt
62.5
57
79
Gold
Au
137
80
Mercury
Hg
119
81
Thallium
Tl
150
82
Lead
Pb
83
Bismuth
Bi
84
Polonium
Po
85
Astatine
At
87
Francium
Fr
88
Radium
Ra
68
80
85
57
102
88.5
119
77.5
103
76
94
67
62
180
148 (8)
39 (4)
Ionic radius
238
89
Actinium
Ac
112
90
Thorium
Th
91
Protactinium
Pa
104
90
78
92
Uranium
102.5
89
76
73
93
Neptunium
Np
101
87
75
72
94
Plutonium
Pu
100
86
74
71
95
Americium
Am
85
96
Curium
Cm
97
85
97
Berkelium
Bk
96
83
98
Californium
Cf
95
82.1
94
110
71
RM
Anion, X
RX
Li+
109.4
Cl-
218.1
Na+
149.7
Br-
237.2
For many compounds, the model of ions as hard spheres does not reproduce the distance between ions,
, to the
accuracy with which it can be measured in crystals. One approach to improving the calculated accuracy is to model
ions as "soft spheres" that overlap in the crystal. Because the ions overlap, their separation in the crystal will be less
than the sum of their soft-sphere radii.[7] The relation between soft-sphere ionic radii,
and
, and
, is
given by
,
where
giving
is an exponent that varies with the type of crystal structure. In the hard-sphere model,
. In the soft-sphere model,
would be 1,
group 1 halides with the sodium chloride structure, a value of 1.6667 gives good agreement with experiment. Some
soft-sphere ionic radii are in the table. These radii are larger than the crystal radii given above (Li+, 90 pm; Cl-, 167
pm).
Observed
Soft-sphere model
LiCl
257.0
257.2
LiBr
275.1
274.4
NaCl
282.0
281.9
NaBr
298.7
298.2
Inter-ionic separations calculated with these radii give remarkably good agreement with experimental values. Some
data are given in the table. Curiously, no theoretical justification for the equation containing has been given.
Ionic radius
Non-spherical Ions
The concept of ionic radii is based on the assumption of a spherical ion shape. However, from a group-theoretical
point of view the assumption is only justified for ions that reside on high-symmetry crystal lattice sites like Na and
Cl in halite or Zn and S in sphalerite. A clear distinction can be made, when the point symmetry group of the
respective lattice site is considered,[8] which are the cubic groups Oh and Td in NaCl and ZnS. For ions on
lower-symmetry sites significant deviations of their electron density from a spherical shape may occur. This holds in
particular for ions on lattice sites of polar symmetry, which are the crystallographic point groups C1, C1h, Cn or Cnv,
n = 2, 3, 4 or 6.[9] A thorough analysis of the bonding geometry was recently carried out for pyrite-type disulfides,
where monovalent sulfur ions reside on C3 lattice sites. It was found that the sulfur ions have to be modeled by
thermal ellipsoids with different radii in direction of the symmetry axis and perpendicular to it.[10] Remarkably, it
turned out in this case that it is not the ionic radius, but the ionic volume that remains constant in different crystalline
compounds.
References
[1] On the basis of conventional ionic radii, Ag+ (129pm) is indeed larger than Na+ (116pm)
[2] Land, A. (1920). "ber die Gre der Atome" (http:/ / springerlink. com/ content/ j862631p43032333/ ). Zeitschrift fr Physik 1 (3):
191197. doi:10.1007/BF01329165. . Retrieved 1 June 2011.
[3] Wasastjerna, J. A. (1923). "On the radii of ions". Comm. Phys.-Math., Soc. Sci. Fenn. 1 (38): 125.
[4] Goldschmidt, V. M. (1926). Geochemische Verteilungsgesetze der Elemente. Skrifter Norske VidenskapsAkad. Oslo, (I) Mat. Natur.. This
is an 8 volume set of books by Goldschmidt.
[5] Pauling, L. (1960). The Nature of the Chemical Bond (3rd Edn.). Ithaca, NY: Cornell University Press.
[6] R. D. Shannon (1976). "Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides". Acta Cryst
A32: 751767. Bibcode1976AcCrA..32..751S. doi:10.1107/S0567739476001551.
[7] Lang, Peter F.; Smith, Barry C. (2010). "Ionic radii for Group 1 and Group 2 halide, hydride, fluoride, oxide, sulfide, selenide and telluride
crystals". Dalton Transactions 39 (33): 77867791. doi:10.1039/C0DT00401D. PMID20664858.
[8] H. Bethe (1929). "Termaufspaltung in Kristallen". Ann. Physik 3 (2): 133208. doi:10.1002/andp.19293950202.
[9] M. Birkholz (1995). "Crystal-field induced dipoles in heteropolar crystals II. Physical significance (http:/ / www. mariobirkholz. de/
ZPB1995b. pdf)"]. Z. Phys. B 96: 333340. Bibcode1995ZPhyB..96..333B. doi:10.1007/BF01313055. .
[10] M. Birkholz, R. Rudert (2008). "Interatomic distances in pyrite-structure disulfides a case for ellipsoidal modelling of sulphur ions" (http:/
/ www. mariobirkholz. de/ pssb2008. pdf). phys. stat. sol. (b) 245: 18581864. Bibcode2008PSSBR.245.1858B.
doi:10.1002/pssb.200879532. .
239
240
where
Z is the number of protons in the nucleus (atomic number), and
S is the average number of electrons between the nucleus and the electron in question (the number of
nonvalence electrons).
S can be found by the systematic application of various rule sets, the simplest of which is known as "Slater's rules"
(named after John C. Slater). Douglas Hartree defined the effective Z of a Hartree-Fock orbital to be:
where
<r>H is the mean radius of the orbital for hydrogen, and
<r>Z is the mean radius of the orbital for an electron configuration with nuclear charge Z.
Note: Zeff is also often written Z*.
241
Example
Consider a sodium cation, a fluorine anion, and a neutral neon atom. Each has 10 electrons, and the number of
nonvalence electrons is 2 (10 total electrons - 8 valence) but the effective nuclear charge varies because each has a
different atomic number:
So, the sodium cation has the largest effective nuclear charge, and thus the smallest atomic radius.
Values
Updated values of screening constants were provided by Clementi et al.[1] [2]
He
1s
1.000
1.688
Li
Be
Ne
10
1s
2.691
3.685
4.680
5.673
6.665
7.658
8.650
9.642
2s
1.279
1.912
2.576
3.217
3.847
4.492
5.128
5.758
2.421
3.136
3.834
4.453
5.100
5.758
2p
Na
Mg
Al
Si
Cl
Ar
11
12
13
14
15
16
17
18
1s 10.626 11.609
2s
6.571
7.392
8.214
9.020
2p
6.802
7.826
8.963
3s
2.507
3.308
4.117
4.903
5.642
6.367
7.068
7.757
4.066
4.285
4.886
5.482
6.116
6.764
3p
Ca
Sc
Ti
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ga
Ge
As
Se
Br
Kr
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
3s
8.680
3p
7.726
8.658
4s
3.495
4.398
4.632
4.817
4.981
5.133
7.120
8.141
8.983
3d
5.283
5.434
5.576
5.711
5.842
5.965
Sr
Zr
Nb
Mo
Tc
Ru
Rh
8.044
8.944
4p
Rb
7.067
Pd
Ag
Cd
6.222
6.780
7.449
8.287
9.028
9.338
In
Sn
Sb
Te
Xe
37
38
39
242
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
5s
4d
4.985
6.071
6.256
6.446
5.921
6.106
7.227
6.485
6.640 (empty)
5p
6.756
8.192
9.102
References
[1] Clementi, E.; Raimondi, D. L. (1963). "Atomic Screening Constants from SCF Functions". J. Chem. Phys 38 (11): 26862689.
Bibcode1963JChPh..38.2686C. doi:10.1063/1.1733573.
[2] Clementi, E.; Raimondi, D. L.; Reinhardt, W. P. (1967). "Atomic Screening Constants from SCF Functions. II. Atoms with 37 to 86
Electrons". Journal of Chemical Physics 47: 13001307. Bibcode1967JChPh..47.1300C. doi:10.1063/1.1712084.
Resources
Brown, Theodore; LeMay, H.E.; & Bursten, Bruce (2002). Chemistry: The Central Science (8th revised edition).
Upper Saddle River, NJ 07458: Prentice-Hall. ISBN 0-61155-61141-5.
Electronegativity
Electronegativity
Electronegativity, symbol (the Greek
letter chi), is a chemical property that
describes the tendency of an atom or a
functional group to attract electrons (or
electron density) towards itself.[1] An atom's
electronegativity is affected by both its
This electrostatic potential map shows how the oxygen atom has a more negative
charge than the hydrogen atoms.
atomic number and the distance that its
valence electrons reside from the charged
nucleus. The higher the associated electronegativity number, the more an element or compound attracts electrons
towards it. First proposed by Linus Pauling in 1932 as a development of valence bond theory,[2] it has been shown to
correlate with a number of other chemical properties. Electronegativity cannot be directly measured and must be
calculated from other atomic or molecular properties. Several methods of calculation have been proposed, and
although there may be small differences in the numerical values of the electronegativity, all methods show the same
periodic trends between elements.
The most commonly used method of calculation is that originally proposed by Linus Pauling. This gives a
dimensionless quantity, commonly referred to as the Pauling scale, on a relative scale running from around 0.7 to
3.98 (hydrogen= 2.20). When other methods of calculation are used, it is conventional (although not obligatory) to
quote the results on a scale that covers the same range of numerical values: this is known as an electronegativity in
Pauling units.
Electronegativity, as it is usually calculated, is not strictly a property of an atom, but rather a property of an atom in a
molecule.[3] Properties of a free atom include ionization energy and electron affinity. It is to be expected that the
electronegativity of an element will vary with its chemical environment,[4] but it is usually considered to be a
transferable property, that is to say that similar values will be valid in a variety of situations.
On the most basic level, electronegativity is determined by factors like the nuclear charge (the more protons an atom
has, the more "pull" it will have on negative electrons) and the number/location of other electrons present in the
atomic shells (the more electrons an atom has, the farther from the nucleus the valence electrons will be, and as a
result the less positive charge they will experience -- both because of their increased distance from the nucleus, and
because the other electrons in the lower energy core orbitals will act to shield the valence electrons from the
positively charged nucleus).
The opposite of electronegativity is electropositivity: a measure of an element's ability to donate electrons.
243
Electronegativity
244
10
11
12
13
14
15
16
17
18
Period (horizontal)
1
H
2.20
He
Li
Be
0.98 1.57
B
C
N
O
F
2.04 2.55 3.04 3.44 3.98
Ne
Na Mg
0.93 1.31
Al
Si
P
S
Cl
1.61 1.90 2.19 2.58 3.16
Ar
K
Ca Sc
Ti
V
Cr Mn Fe Co Ni Cu Zn Ga Ge As Se
Br Kr
0.82 1.00 1.36 1.54 1.63 1.66 1.55 1.83 1.88 1.91 1.90 1.65 1.81 2.01 2.18 2.55 2.96 3.00
Rb Sr
Y
Zr
0.82 0.95 1.22 1.33
Nb
1.6
Mo
2.16
Tc
1.9
Ru
2.2
Rh Pd Ag Cd
In
Sn Sb
2.28 2.20 1.93 1.69 1.78 1.96 2.05
Te
2.1
I
Xe
2.66 2.60
Cs Ba
0.79 0.89
Hf
1.3
Ta
1.5
W
2.36
Re
1.9
Os
2.2
Ir
Pt Au Hg Tl
Pb
Bi
2.20 2.28 2.54 2.00 1.62 2.33 2.02
Po
2.0
At
2.2
Fr
0.7
Ra
0.9
**
Rf
Db
Sg
Bh
Hs
Mt
Ds
Rg
Lanthanoids
La
1.1
Ce
Pr Nd Pm Sm
1.12 1.13 1.14 1.13 1.17
Eu
1.2
Gd
1.2
Tb
1.1
Dy Ho Er Tm
1.22 1.23 1.24 1.25
Yb
1.1
Lu
1.27
Actinoids
**
Ac
1.1
Th
1.3
U
Np Pu Am Cm
1.38 1.36 1.28 1.13 1.28
Bk
1.3
Cf
1.3
No
1.3
Lr
1.3
Pa
1.5
Cn
Es
1.3
Rn
2.2
Fm
1.3
Md
1.3
Methods of calculation
Pauling electronegativity
Pauling first proposed[2] the concept of electronegativity in 1932 as an explanation of the fact that the covalent bond
between two different atoms (AB) is stronger than would be expected by taking the average of the strengths of the
AA and BB bonds. According to valence bond theory, of which Pauling was a notable proponent, this "additional
stabilization" of the heteronuclear bond is due to the contribution of ionic canonical forms to the bonding.
The difference in electronegativity between atoms A and B is given by:
where the dissociation energies, Ed, of the AB, AA and BB bonds are expressed in electronvolts, the factor
(eV) being included to ensure a dimensionless result. Hence, the difference in Pauling electronegativity between
hydrogen and bromine is 0.73 (dissociation energies: HBr, 3.79eV; HH, 4.52eV; BrBr 2.00eV)
As only differences in electronegativity are defined, it is necessary to choose an arbitrary reference point in order to
construct a scale. Hydrogen was chosen as the reference, as it forms covalent bonds with a large variety of elements:
its electronegativity was fixed first[2] at 2.1, later revised[5] to 2.20. It is also necessary to decide which of the two
elements is the more electronegative (equivalent to choosing one of the two possible signs for the square root). This
is done by "chemical intuition": in the above example, hydrogen bromide dissolves in water to form H+ and Br ions,
so it may be assumed that bromine is more electronegative than hydrogen.
Electronegativity
245
To calculate Pauling electronegativity for an element, it is necessary to have data on the dissociation energies of at
least two types of covalent bond formed by that element. Allred updated Pauling's original values in 1961 to take
account of the greater availability of thermodynamic data,[5] and it is these "revised Pauling" values of the
electronegativity which are most usually used.
Mulliken electronegativity
Mulliken proposed that the arithmetic mean
of the first ionization energy (Ei) and the
electron affinity (Eea) should be a measure
of the tendency of an atom to attract
electrons.[6] [7] As this definition is not
dependent on an arbitrary relative scale, it
has
also
been
termed
absolute
[8]
electronegativity,
with the units of
kilojoules per mole or electronvolts.
However, it is more usual to use a linear transformation to transform these absolute values into values which
resemble the more familiar Pauling values. For ionization energies and electron affinities in electronvolts,[9]
and for energies in kilojoules per mole,[10]
The Mulliken electronegativity can only be calculated for an element for which the electron affinity is known,
fifty-seven elements as of 2006. The Mulliken electronegativity of an atom is sometimes said to be the negative of
the chemical potential. By inserting the energetic definitions of the ionization potential and electron affinity into the
Mulliken electronegativity, it is possible to show that the Mulliken chemical potential is a finite difference
approximation of the electronic energy with respect to the number of electrons., i.e.,
Electronegativity
246
AllredRochow electronegativity
Allred and Rochow considered[11] that
electronegativity should be related to the
charge experienced by an electron on the
"surface" of an atom: the higher the charge
per unit area of atomic surface, the greater
the tendency of that atom to attract
electrons. The effective nuclear charge,
Z*experienced by valence electrons can be
estimated using Slater's rules, while the
surface area of an atom in a molecule can be
taken to be proportional to the square of the
covalent radius, rcov. When rcov is expressed
in angstroms,
Electronegativity
247
Allen electronegativity
Perhaps the simplest definition of
electronegativity is that of Allen, who has
proposed that it is related to the average
energy of the valence electrons in a free
atom,[18]
where s,p are the one-electron energies of s- and p-electrons in the free atom and ns,p are the number of s- and
p-electrons in the valence shell. It is usual to apply a scaling factor, 1.75103 for energies expressed in kilojoules
per mole or 0.169 for energies measured in electronvolts, to give values which are numerically similar to Pauling
electronegativities.
The one-electron energies can be determined directly from spectroscopic data, and so electronegativities calculated
by this method are sometimes referred to as spectroscopic electronegativities. The necessary data are available for
almost all elements, and this method allows the estimation of electronegativities for elements which cannot be
treated by the other methods, e.g. francium, which has an Allen electronegativity of 0.67.[19] However, it is not clear
what should be considered to be valence electrons for the d- and f-block elements, which leads to an ambiguity for
their electronegativities calculated by the Allen method.
In this scale neon has the highest electronegativity of all elements, followed by fluorine, helium and oxygen.
Group (vertical)
10
11
12
13
14
15
16
17
18
Period (horizontal)
1
H
2.300
He
4.160
Li
Be
0.912 1.576
B
C
N
O
F
Ne
2.051 2.544 3.066 3.610 4.193 4.789
Na
Mg
0.869 1.293
Al
Si
P
S
Cl
Ar
1.613 1.916 2.253 2.589 2.869 3.242
K
Ca
Sc
Ti
V
Cr Mn Fe Co Ni Cu Zn
Ga
Ge
As
Se
Br
Kr
0.734 1.034 1.19 1.38 1.53 1.65 1.75 1.80 1.84 1.88 1.85 1.59 1.756 1.994 2.211 2.434 2.685 2.966
Rb
Sr
Y
Zr Nb Mo Tc Ru Rh Pd Ag Cd
In
Sn
Sb
Te
I
Xe
0.706 0.963 1.12 1.32 1.41 1.47 1.51 1.54 1.56 1.59 1.87 1.52 1.656 1.824 1.984 2.158 2.359 2.582
Cs
Ba
Lu Hf Ta
W Re Os
Ir
Pt Au Hg
Tl
Pb
0.659 0.881 1.09 1.16 1.34 1.47 1.60 1.65 1.68 1.72 1.92 1.76 1.789 1.854
Fr
0.67
Ra
0.89
**
Bi
2.01
Po
2.19
At
2.39
Rn
2.60
Electronegativity
248
Periodic table of electronegativity using the Allen scale
List of various electronegativities of main group elements
See also Electronegativities of the elements (data page) and List of electronegativities
Electronegativity
Trends in electronegativity
Periodic trends
In general, electronegativity increases on
passing from left to right along a period, and
decreases on descending a group. Hence,
fluorine is undoubtedly the most
electronegative of the elements (not
counting noble gases) while caesium is the
least electronegative, at least of those
elements for which substantial data is
available.[19]
There are some exceptions to this general
rule. Gallium and germanium have higher
electronegativities than aluminium and
silicon respectively because of the d-block
The variation of Pauling electronegativity (y-axis) as one descends the main groups
contraction. Elements of the fourth period
of the Periodic table from the second period to the sixth period.
immediately after the first row of the
transition metals have unusually small
atomic radii because the 3d-electrons are not effective at shielding the increased nuclear charge, and smaller atomic
size correlates with higher electronegativity (see Allred-Rochow electronegativity, Sanderson electronegativity
above). The anomalously high electronegativity of lead, particularly when compared to thallium and bismuth,
appears to be an artifact of data selection (and data availability)methods of calculation other than the Pauling
method show the normal periodic trends for these elements.
249
Electronegativity
250
Acid
Hypochlorous acid
HClO
+1
+7.5
Chlorous acid
HClO2
+3
+2.0
Chloric acid
HClO3
+5
1.0
Perchloric acid
HClO4
+7
10
The chemical effects of this increase in electronegativity can be seen both in the structures of oxides and halides and
in the acidity of oxides and oxoacids. Hence CrO3 and Mn2O7 are acidic oxides with low melting points, while
Cr2O3 is amphoteric and Mn2O3 is a completely basic oxide.
The effect can also be clearly seen in the dissociation constants of the oxoacids of chlorine. The effect is much larger
than could be explained by the negative charge being shared among a larger number of oxygen atoms, which would
lead to a difference in pKa of log10()= 0.6 between hypochlorous acid and perchloric acid. As the oxidation state
of the central chlorine atom increases, more electron density is drawn from the oxygen atoms onto the chlorine,
reducing the partial negative charge on the oxygen atoms and increasing the acidity.
Group electronegativity
In organic chemistry, electronegativity is associated more with different functional groups than with individual
atoms. The terms group electronegativity and substituent electronegativity are used synonymously. However, it is
common to distinguish between the inductive effect and the resonance effect, which might be described as - and
-electronegativities respectively. There are a number of linear free-energy relationships which have been used to
quantify these effects, of which the Hammett equation is the best known. Kabachnik parameters are group
electronegativities for use in organophosphorus chemistry.
Electropositivity
Electropositivity is a measure of an element's ability to donate electrons, and therefore form positive ions; thus, it is
opposed to electronegativity. Mainly, this is an attribute of metals, meaning that for the most part, the greater the
metallic character of an element, the greater the electropositivity. Therefore the alkali metals are most electropositive
of all. This is because they have a single electron in their outer shell and, as this is relatively far from the nucleus of
the atom, it is easily lost; in other words, these metals have low ionization energies.[23]
While electronegativity increases along periods in the periodic table, and decreases down groups, electropositivity
decreases along periods (from left to right) and increases down groups.
Electropositive shark repellent utilizes electropositive metals as shark repellents, since they generate measurable
voltages in a seawater electrolyte relative to a shark.
Electronegativity
References
[1] IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006) " Electronegativity
(http:/ / goldbook. iupac. org/ E01990. html)".
[2] Pauling, L. (1932). "The Nature of the Chemical Bond. IV. The Energy of Single Bonds and the Relative Electronegativity of Atoms".
Journal of the American Chemical Society 54 (9): 35703582. doi:10.1021/ja01348a011.
[3] Pauling, Linus (1960). Nature of the Chemical Bond. Cornell University Press. pp.88107. ISBN0801403332.
[4] Greenwood, N. N.; Earnshaw, A. (1984). Chemistry of the Elements. Pergamon. p.30. ISBN0-08-022057-6.
[5] Allred, A. L. (1961). "Electronegativity values from thermochemical data". Journal of Inorganic and Nuclear Chemistry 17 (34): 215221.
doi:10.1016/0022-1902(61)80142-5.
[6] Mulliken, R. S. (1934). "A New Electroaffinity Scale; Together with Data on Valence States and on Valence Ionization Potentials and
Electron Affinities". Journal of Chemical Physics 2 (11): 782793. doi:10.1063/1.1749394.
[7] Mulliken, R. S. (1935). "Electronic Structures of Molecules XI. Electroaffinity, Molecular Orbitals and Dipole Moments". J. Chem. Phys. 3
(9): 573585. doi:10.1063/1.1749731.
[8] Pearson, R. G. (1985). "Absolute electronegativity and absolute hardness of Lewis acids and bases". J. Am. Chem. Soc. 107 (24): 6801.
doi:10.1021/ja00310a009.
[9] Huheey, J. E. (1978). Inorganic Chemistry (2nd Edn.). New York: Harper & Row. p.167.
[10] This second relation has been recalculated using the best values of the first ionization energies and electron affinities available in 2006.
[11] Allred, A. L.; Rochow, E. G. (1958). "A scale of electronegativity based on electrostatic force". Journal of Inorganic and Nuclear Chemistry
5 (4): 264. doi:10.1016/0022-1902(58)80003-2.
[12] Sanderson, R. T. (1983). "Electronegativity and bond energy". Journal of the American Chemical Society 105 (8): 2259.
doi:10.1021/ja00346a026.
[13] Sanderson, R. T. (1983). Polar Covalence. New York: Academic Press. ISBN0126180806.
[14] Zefirov, N. S.; M. A. Kirpichenok, F. F. Izmailov, and M. I. Trofimov (1987). Doklady Akademii Nauk SSSR 296: 883.
[15] Trofimov, M. I.; Smolenskii, E. A. (2005). "Application of the electronegativity indices of organic molecules to tasks of chemical
informatics". Russian Chemical Bulletin 54 (9): 2235. doi:10.1007/s11172-006-0105-6.
[16] SW Rick &SJ Stuart (2002). "Electronegativity equalization models" (http:/ / books. google. com/ ?id=IqWXSLz6QE8C& pg=PA106). In
Kenny B. Lipkowitz, Donald B. Boyd. Reviews in computational chemistry. Wiley. p.106. ISBN0471215767. .
[17] Robert G. Parr, Weitao Yang (1994). Density-functional theory of atoms and molecules (http:/ / books. google. com/
?id=mGOpScSIwU4C& pg=PA91). Oxford University Press. p.91. ISBN0195092767. .
[18] Allen, Leland C. (1989). "Electronegativity is the average one-electron energy of the valence-shell electrons in ground-state free atoms".
Journal of the American Chemical Society 111 (25): 9003. doi:10.1021/ja00207a003.
[19] The widely quoted Pauling electronegativity of 0.7 for francium is an extrapolated value of uncertain provenance. The Allen
electronegativity of caesium is 0.66.
[20] See, e.g., Bellamy, L. J. (1958). The Infra-Red Spectra of Complex Molecules. New York: Wiley. p.392. ISBN0412138506.
[21] Spieseke, H.; Schneider, W. G. (1961). "Effect of Electronegativity and Magnetic Anisotropy of Substituents on C13 and H1 Chemical
Shifts in CH3X and CH3CH2X Compounds". Journal of Chemical Physics 35 (2): 722. doi:10.1063/1.1731992.
[22] Clasen, C. A.; Good, M. L. (1970). "Interpretation of the Moessbauer spectra of mixed-hexahalo complexes of tin(IV)". Inorganic
Chemistry 9 (4): 817. doi:10.1021/ic50086a025.
[23] " Electropositivity (http:/ / www. webcitation. org/ 5kwpIKRbL)," Microsoft Encarta Online Encyclopedia 2009. (Archived 2009-10-31)
External links
WebElements (http://www.webelements.com/), lists values of electronegativities by a number of different
methods of calculation
Video explaining electronegativity (http://sciencehack.com/videos/view/6952235798166539784)
Bibliography
Jolly, William L. (1991). Modern Inorganic Chemistry (2nd ed.). New York: McGraw-Hill. pp.7176.
ISBN0-07-112651-1.
Mullay, J. (1987). "Estimation of atomic and group electronegativities". Structure and Bonding. Structure and
Bonding 66: 125. doi:10.1007/BFb0029834. ISBN3-540-17740-X.
251
Mole
Mole
The mole is a unit of measurement used in chemistry to express amounts of a chemical substance, defined as an
amount of a substance that contains as many elementary entities (e.g., atoms, molecules, ions, electrons) as there are
atoms in 12 grams of pure carbon-12 (12C), the isotope of carbon with atomic weight 12. This corresponds to a value
of 6.02214179(30)1023 elementary entities of that substance. It is one of the base units in the International System
of Units, and has the unit symbol mol.[1]
The mole is widely used in chemistry, instead of units of mass or volume, as a convenient way to express the
amounts of reagents and products of chemical reactions. For example, the chemical equation 2 H2 + O2 2 H2O
implies that 2mol of dihydrogen and 1mol of dioxygen react to form 2mol of water. The mole may also be used to
express the number of atoms, ions, or other elementary entities in some sample. The concentration of a solution is
commonly expressed by its molarity, the number of moles of the dissolved substance per liter of solution.
The number of molecules in a mole (known as Avogadro's number) is defined so that the mass of one mole of a
substance, expressed in grams, is exactly equal to the substance's mean molecular weight. For example, the mean
molecular weight of natural water is about 18.015, so one mole of water is about 18.015grams. This property
considerably simplifies many chemical and physical computations.
The name gram-molecule was formerly used for essentially the same concept.[1] The name gram-atom (abbreviated
gat.) has been used for related but distinct concept, namely a quantity of a substance that contains Avogadro's
number of atoms, whether isolated or combined in molecules. Thus, for example, 1 mole of MgB2 is
1gram-molecule of MgB2 but 3gram-atoms of MgB2.[2] [3]
252
Mole
253
History
The history of the mole is intertwined with that of molecular mass, atomic mass unit, Avogadro's number and related
concepts.
The first table of atomic weights was published by John Dalton (17661844) in 1805, based on a system in which
the atomic weight of hydrogen was defined as 1. These atomic weights were based on the stoichiometric proportions
of chemical reactions and compounds, a fact that greatly aided their acceptance: It was not necessary for a chemist to
subscribe to atomic theory (an unproven hypothesis at the time) to make practical use of the tables. This would lead
to some confusion between atomic weights (promoted by proponents of atomic theory) and equivalent weights
(promoted by its opponents and which sometimes differed from atomic weights by an integer factor), which would
last throughout much of the nineteenth century.
Jns Jacob Berzelius (17791848) was instrumental in the determination of atomic weights to ever-increasing
accuracy. He was also the first chemist to use oxygen as the standard to which other weights were referred. Oxygen
is a useful standard, as, unlike hydrogen, it forms compounds with most other elements, especially metals. However,
he chose to fix the atomic weight of oxygen as 100, an innovation that did not catch on.
Charles Frdric Gerhardt (181656), Henri Victor Regnault (181078) and Stanislao Cannizzaro (18261910)
expanded on Berzelius' works, resolving many of the problems of unknown stoichiometry of compounds, and the use
of atomic weights attracted a large consensus by the time of the Karlsruhe Congress (1860). The convention had
reverted to defining the atomic weight of hydrogen as 1, although at the level of precision of measurements at that
time relative uncertainties of around 1% this was numerically equivalent to the later standard of oxygen = 16.
However the chemical convenience of having oxygen as the primary atomic weight standard became ever more
evident with advances in analytical chemistry and the need for ever more accurate atomic weight determinations.
Developments in mass spectrometry led to the adoption of oxygen-16 as the standard substance, in lieu of natural
oxygen. The current definition of the mole, based on carbon-12, was approved during the 1960s.[1] [7] The four
different definitions were equivalent to within 1%.
Scale basis
Scale basis
Relative deviation
relative to 12C = 12 from the 12C = 12 scale
1.00794(7)
0.788%
15.9994(3)
+0.00375%
+0.0318%
The name mole is an 1897 translation of the German unit Mol, coined by the chemist Wilhelm Ostwald in 1894 from
the German word Molekl (molecule).[8] [9] [10] However, the related concept of equivalent mass had been in use at
least a century earlier.[11]
Mole
254
the SI defines numbers of entities as quantities of dimension one, and thus ignores the ontological distinction
between entities and units of continuous quantities.[15]
In chemistry, it has been known since Proust's law of definite proportions (1794) that knowledge of the mass of each
of the components in a chemical system is not sufficient to define the system. Amount of substance can be described
as mass divided by Proust's "definite proportions", and contains information that is missing from the measurement of
mass alone. As demonstrated by Dalton's law of partial pressures (1803), a measurement of mass is not even
necessary to measure the amount of substance (although in practice it is usual). There are many physical
relationships between amount of substance and other physical quantities, the most notable one being the ideal gas
law (where the relationship was first demonstrated in 1857). The term "mole" was first used in a textbook describing
these colligative properties.
Related units
The SI units for molar concentration are mol/m3. However, most chemical literature traditionally uses mol/dm3, or
mol dm3, which is the same as mol/L. These traditional units are often denoted by a capital letter M (pronounced
"molar"), sometimes preceded by an SI prefix, for example, millimoles per litre (mmol/L) or millimolar (mM),
micromoles/litre (mol/L) or micromolar (M), or nanomoles/L (nmol/L) or nanomolar (nM).
Mole
References
[1] International Bureau of Weights and Measures (2006), The International System of Units (SI) (http:/ / www. bipm. org/ utils/ common/ pdf/
si_brochure_8_en. pdf) (8th ed.), pp.11415, ISBN92-822-2213-6,
[2] Wang, Yuxing et al.; Bouquet, Fr d ric; Sheikin, Ilya; Toulemonde, Pierre; Revaz, Bernard; Eisterer, Michael; Weber, Harald W; Hinderer,
Joerg et al. (2003). "Specific heat of MgB2 after irradiation". Journal of Physics: Condensed Matter 15 (6): 883893.
arXiv:cond-mat/0208169. Bibcode2003JPCM...15..883W. doi:10.1088/0953-8984/15/6/315.
[3] Lortz, R. et al.; Wang, Y.; Abe, S.; Meingast, C.; Paderno, Yu.; Filippov, V.; Junod, A. (2005). "Specific heat, magnetic susceptibility,
resistivity and thermal expansion of the superconductor ZrB12". Phys. Rev. B 72 (2): 024547. arXiv:cond-mat/0502193.
Bibcode2005PhRvB..72b4547L. doi:10.1103/PhysRevB.72.024547.
[4] International Bureau of Weights and Measures. " Realising the mole (http:/ / www. bipm. org/ utils/ en/ pdf/ SIApp2_mol_en. pdf)."
Retrieved 25 September 2008.
[5] Mohr, Peter J.; Taylor, Barry N.; Newell, David B. (2008). "CODATA Recommended Values of the Fundamental Physical Constants: 2006"
(http:/ / physics. nist. gov/ cuu/ Constants/ codata. pdf). Rev. Mod. Phys. 80: 633730. Bibcode2008RvMP...80..633M.
doi:10.1103/RevModPhys.80.633. . Direct link to value (http:/ / physics. nist. gov/ cgi-bin/ cuu/ Value?na).
[6] Andreas, Birk; et al (2011). "Determination of the Avogadro Constant by Counting the Atoms in a 28Si Crystal" (http:/ / physics. aps. org/
synopsis-for/ 10. 1103/ PhysRevLett. 106. 030801). Physical Review Letters 106 (3). Bibcode2011PhRvL.106c0801A.
doi:10.1103/PhysRevLett.106.030801. .
[7] de Bivre, P.; Peiser, H.S. (1992). "'Atomic Weight'The Name, Its History, Definition, and Units" (http:/ / www. iupac. org/ publications/
pac/ 1992/ pdf/ 6410x1535. pdf). Pure Appl. Chem. 64 (10): 153543. doi:10.1351/pac199264101535.
[8] Helm, Georg (1897). The Principles of Mathematical Chemistry: The Energetics of Chemical Phenomena. transl. by Livingston, J.; Morgan,
R.. New York: Wiley. p. 6.
[9] Some sources place the date of first usage in English as 1902. MerriamWebster proposes (http:/ / www. merriam-webster. com/ dictionary/
mole[5]) an etymology from Molekulrgewicht (molecular weight).
[10] Ostwald, Wilhelm (1893). Hand- und Hilfsbuch zur Ausfhrung Physiko-Chemischer Messungen. Leipzig. p.119.
[11] mole, n.8, Oxford English Dictionary, Draft Revision Dec. 2008
[12] Price, Gary (2010). "Failures of the global measurement system. Part 1: the case of chemistry" (http:/ / www. springerlink. com/ content/
p63w663v127t5g0q/ ). Accreditation and Quality Assurance 15 (7): 421427. doi:10.1007/s00769-010-0655-z. ..
[13] Johansson, Ingvar (2010). "Metrological thinking needs the notions of parametric quantities, units, and dimensions." (http:/ / stacks. iop.
org/ 0026-1394/ 47/ i=3/ a=012). Metrologia 47 (3): 219230. Bibcode2010Metro..47..219J. doi:10.1088/0026-1394/47/3/012. .
[14] Furio, C; Azcona, R;Guisasola, J. (2002). "The learning and teaching of the concepts 'amount of substance' and mole - a review of the
literature" (http:/ / www. uoi. gr/ cerp/ 2002_October/ pdf/ 02Furio. pdf). Chemistry Education: Research and Practice in Europe 3 (3):
277292. .
[15] Cooper, G; Humphry, S (2010). "The ontological distinction between units and entities". Synthese. doi:10.1007/s11229-010-9832-1.
[16] In particular, when the mole is used, alongside the SI unit of volume of a cubic metre, in thermodynamic calculations such as the ideal gas
law, a factor of 1000 is introduced which engineering practice chooses to simplify by adopting the kilomole.
[17] Himmelblau, David (1996). Basic Principles and Calculations in Chemical Engineering (6 ed.). pp.1720. ISBN0-13-305798-4.
[18] Mills, Ian M.; Mohr, Peter J.; Quinn, Terry J.; Taylor, Barry N.; Williams, Edwin R. (2005). "Redefinition of the kilogram: a decision whose
time has come" (http:/ / www. iop. org/ EJ/ article/ 0026-1394/ 42/ 2/ 001/ met5_2_001. pdf). Metrologia 42 (2): 7180.
Bibcode2005Metro..42...71M. doi:10.1088/0026-1394/42/2/001. . Abstract (http:/ / www. iop. org/ EJ/ abstract/ 0026-1394/ 42/ 2/ 001/ ).
[19] History of National Mole Day Foundation, Inc (http:/ / www. moleday. org/ htdocs/ history. html)
External links
ChemTeam: The Origin of the Word 'Mole' (http://web.archive.org/20071222072256/http://dbhs.wvusd.
k12.ca.us/webdocs/Mole/Origin-of-Mole.html) at the Wayback Machine (archived December 22, 2007)
255
Lewis structure
256
Lewis structure
Lewis structures (also known as Lewis dot diagrams, electron dot diagrams, and
electron dot structures) are diagrams that show the bonding between atoms of a
molecule and the lone pairs of electrons that may exist in the molecule.[1] [2] [3] A Lewis
structure can be drawn for any covalently bonded molecule, as well as coordination
compounds. The Lewis structure was named after Gilbert Newton Lewis, who
introduced it in his 1916 article The Atom and the Molecule.[4] They are similar to
electron dot diagrams in that the valence electrons in lone pairs are represented as dots,
but they also contain lines to represent shared pairs in a chemical bond (single, double,
triple, etc.).
Lewis structures show each atom and its position in the structure of the molecule using its chemical symbol. Lines
are drawn between atoms that are bonded to one another (pairs of dots can be used instead of lines). Excess electrons
that form lone pairs are represented as pairs of dots, and are placed next to the atoms.
Although many of the elements react by gaining, losing or sharing electrons until they have achieved a valence shell
electron configuration with a full octet (8) of electrons, there are many noteworthy exceptions to the 'octet rule'.
Hydrogen(H) conforms instead to a duet rule wherein it fills its first (and outermost) shell with just two electrons or
empties it completely. Some compounds like boron trifluoride have incomplete orbitals while other such as sulphur
hexafluoride have valence shell with more than eight electrons.
Placing electrons
Once the total number of available
electrons has been determined,
electrons must be placed into the
structure. They should be placed
initially as lone pairs: one pair of dots
for each pair of electrons available.
Lone pairs should initially be placed
on outer atoms (other than hydrogen)
until each outer atom has eight
Lewis structures for oxygen, fluorine, the hydrogen sulfate anion, and formamide
electrons in bonding pairs and lone
pairs; extra lone pairs may then be
placed on the central atom. When in doubt, lone pairs should be placed on more electronegative atoms first.
Lewis structure
Once all lone pairs are placed, atoms, especially the central atoms, may not have an octet of electrons. In this case,
the atoms must form a double bond; a lone pair of electrons is moved to form a second bond between the two atoms.
As the bonding pair is shared between the two atoms, the atom that originally had the lone pair still has an octet; the
other atom now has two more electrons in its valence shell.
Aside from organic compounds, only a minority of compounds have an octet of electrons. Incomplete octets are
common for compounds of groups 2 and 13 such as beryllium, boron, and aluminium. Compounds with more than
eight electrons in the Lewis representation of the valence shell of an atom are called hypervalent, and are common
for elements of groups 15 to 18, such as phosphorus, sulfur, iodine, and xenon.
Lewis structures for polyatomic ions may be drawn by the same method. When counting electrons, negative ions
should have extra electrons placed in their Lewis structures; positive ions should have fewer electrons than an
uncharged molecule.
When the Lewis structure of an ion is written, the entire structure is placed in brackets, and the charge is written as a
superscript on the upper right, outside the brackets.
A simpler method has been proposed for constructing Lewis structures eliminating the need for electron counting:
the atoms are drawn showing the valence electrons, bonds are then formed by pairing up valence electrons of the
atoms involved in the bond-making process and anions and cations are formed by adding or removing electrons
to/from the appropriate atoms.[5]
A trick is to count up valence electrons, then count up the number of electrons needed to complete the octet rule (or
with Hydrogen just 2 electrons), then take the difference of these two numbers and your answer is the number of
electrons that make up the bonds. The rest of the electrons just go and fill all the other atoms' octets.
Formal charge
In terms of Lewis structures, formal charge is used in the description, comparison and assessment of likely
topological and resonance structures[6] by determining the apparent electronic charge of each atom within, based
upon its electron dot structure assuming exclusive covalency or non-polar bonding. It has uses in determining
possible electron re-configuration when referring to reaction mechanisms, and often results in the same sign as the
partial charge of the atom, with exceptions. In general, the formal charge of an atom can be calculated using the
following formula, assuming non-standard definitions for the markup used:
where:
The formal charge of an atom is computed as the difference between the number of valence electrons that a neutral
atom would have and the number of electrons that belong to it in the Lewis structure. Electrons in covalent bonds are
split equally between the atoms involved in the bond. The total of the formal charges on an ion should be equal to the
charge on the ion, and the total of the formal charges on a neutral molecule should be equal to zero.
257
Lewis structure
Resonance
For some molecules and ions, it is difficult to determine which lone pairs should be moved to form double or triple
bonds. This is sometimes the case when multiple atoms of the same type surround the central atom, and is especially
common for polyatomic ions.
When this situation occurs, the molecule's Lewis structure is said to be a resonance structure, and the molecule exists
as a resonance hybrid. Each of the different possibilities is superimposed on the others, and the molecule is
considered to have a Lewis structure equivalent to an average of these states.
The nitrate ion (NO3-), for instance, must form a double bond between nitrogen and one of the oxygens to satisfy the
octet rule for nitrogen. However, because the molecule is symmetrical, it does not matter which of the oxygens forms
the double bond. In this case, there are three possible resonance structures. Expressing resonance when drawing
Lewis structures may be done either by drawing each of the possible resonance forms and placing double-headed
arrows between them or by using dashed lines to represent the partial bonds.
When comparing resonance structures for the same molecule, usually those with the fewest formal charges
contribute more to the overall resonance hybrid. When formal charges are necessary, resonance structures that have
negative charges on the more electronegative elements and positive charges on the less electronegative elements are
favored.
The resonance structure should not be interpreted to indicate that the molecule switches between forms, but that the
molecule acts as the average of multiple forms.
258
Lewis structure
259
Alternative formats
Chemical structures may be written in more compact forms,
particularly when showing organic molecules. In condensed structural
formulas, many or even all of the covalent bonds may be left out, with
subscripts indicating the number of identical groups attached to a
particular atom. Another shorthand structural diagram is the skeletal
formula (also known as a bond-line formula or carbon skeleton
diagram). In skeletal formulae, carbon atoms are not signified by the
symbol C but by the vertices of the lines. Hydrogen atoms bonded to
carbon are not shown they can be inferred by counting the number
of bonds to a particular carbon atom each carbon is assumed to have
four bonds in total, so any bonds not shown are, by implication, to
hydrogen atoms.
Other diagrams may be more complex than Lewis structures, showing
bonds in 3D using various forms such as space filling diagrams.
References
[1] IUPAC definition of Lewis formula (http:/ / goldbook. iupac. org/ L03513. html)
[2] Zumdahl, S. (2005) Chemical Principles Houghton-Mifflin (ISBN 0-618-37206-7)
[3] Miessler, G. L., Tar, D. A., (2003) "Inorganic Chemistry" 2nd ed. Pearson
Prentice-Hall (ISBN 0-130-35471-6)
[4] Lewis, G. N. The Atom and the Molecule. J. Am. Chem. Soc. 1916, 38, 762-785.
doi:10.1021/ja02261a002
[5] Simplified Lewis Structure Drawing for Non-science Majors Miburo, Barnabe B. J.
Chem. Educ. 1993 75 317. Link (http:/ / www. jce. divched. org/ Journal/ Issues/
1998/ Mar/ abs317. html)
[6] Miessler, G. L., Tar, D. A., (2003), p53 - Explanation of formal charge usage.
Chemical bond
260
Chemical bond
A chemical bond is an attraction between atoms that allows the formation of chemical substances that contain two
or more atoms. The bond is caused by the electromagnetic force attraction between opposite charges, either between
electrons and nuclei, or as the result of a dipole attraction. The strength of chemical bonds varies considerably; there
are "strong bonds" such as covalent or ionic bonds and "weak bonds" such as dipole-dipole interactions, the London
dispersion force and hydrogen bonding.
Since opposite charges attract via a simple electromagnetic force, the negatively charged electrons that are orbiting
the nucleus and the positively charged protons in the nucleus attract each other. Also, an electron positioned between
two nuclei will be attracted to both of them. Thus, the most stable configuration of nuclei and electrons is one in
which the electrons spend more time between nuclei, than anywhere else in space. These electrons cause the nuclei
to be attracted to each other, and this attraction results in the bond. However, this assembly cannot collapse to a size
dictated by the volumes of these individual particles. Due to the matter wave nature of electrons and their smaller
mass, they occupy a much larger amount of volume compared with the nuclei, and this volume occupied by the
electrons keeps the atomic nuclei relatively far apart, as compared with the size of the nuclei themselves.
In general, strong chemical bonding is associated with the sharing or transfer of electrons between the participating
atoms. The atoms in molecules, crystals, metals and diatomic gases indeed most of the physical environment
around us are held together by chemical bonds, which dictate the structure and the bulk properties of matter.
Chemical bond
identifiable atoms, and have a direction in space, allowing them to be shown as single connecting lines between
atoms in drawings, or modeled as sticks between spheres in models. In a polar covalent bond, one or more electrons
are unequally shared between two nuclei. Covalent bonds often result in the formation of small collections of
better-connected atoms called molecules, which in solids and liquids are bound to other molecules by forces that are
often much weaker than the covalent bonds that hold the molecules internally together. Such weak intermolecular
bonds give organic molecular substances, such as waxes and oils, their soft bulk character, and their low melting
points (in liquids, molecules must cease most structured or oriented contact with each other). When covalent bonds
link long chains of atoms in large molecules, however (as in polymers such as nylon), or when covalent bonds
extend in networks though solids that are not composed of discrete molecules (such as diamond or quartz or the
silicate minerals in many types of rock) then the structures that result may be both strong and tough, at least in the
direction oriented correctly with networks of covalent bonds. Also, the melting points of such covalent polymers and
networks increase greatly.
In a simplified view of an ionic bond, the bonding electron is not shared at all, but transferred. In this type of bond,
the outer atomic orbital of one atom has a vacancy which allows addition of one or more electrons. These newly
added electrons potentially occupy a lower energy-state (effectively closer to more nuclear charge) than they
experience in a different atom. Thus, one nucleus offers a more tightly bound position to an electron than does
another nucleus, with the result that one atom may transfer an electron to the other. This transfer causes one atom to
assume a net positive charge, and the other to assume a net negative charge. The bond then results from electrostatic
attraction between atoms, and the atoms become positive or negatively charged ions. Ionic bonds may be seen as
extreme examples of polarization in covalent bonds. Often, such bonds have no particular orientation in space, since
they result from equal electrostatic attraction of each ion to all ions around them. Ionic bonds are strong (and thus
ionic substances require high temperatures to melt) but also brittle, since the forces between ions are short-range, and
do not easily bridge cracks and fractures. This type of bond gives a charactistic physical character to crystals of
classic mineral salts, such as table salt.
A less often mentioned type of bonding is the metallic bond. In this type of bonding, each atom in a metal donates
one or more electrons to a "sea" of electrons that reside between many metal atoms. In this sea, each electron is free
(by virtue of its wave nature) to be associated with a great many atoms at once. The bond results because the metal
atoms become somewhat positively charged due to loss of their electrons, while the electrons remain attracted to
many atoms, without being part of any given atom. Metallic bonding may be seen as an extreme example of
delocalization of electrons over a large system of covalent bonds, in which every atom participates. This type of
bonding is often very strong (resulting in the tensile strength of metals). However, metallic bonds are more collective
in nature than other types, and so they allow metal crystals to more easily deform, because they are composed of
atoms attracted to each other, but not in any particularly-oriented ways. This results in the malliability of metals. The
sea of electrons in metallic bonds causes the characteristically good electrical and thermal conductivity of metals,
and also their "shiny" reflection of most frequencies of white light.
All bonds can be explained by quantum theory, but, in practice, simplification rules allow chemists to predict the
strength, directionality, and polarity of bonds. The octet rule and VSEPR theory are two examples. More
sophisticated theories are valence bond theory which includes orbital hybridization and resonance, and the linear
combination of atomic orbitals molecular orbital method which includes ligand field theory. Electrostatics are used
to describe bond polarities and the effects they have on chemical substances.
261
Chemical bond
History
Early speculations into the nature of the chemical bond, from as early as the 12th century, supposed that certain
types of chemical species were joined by a type of chemical affinity. In 1704, Isaac Newton famously outlined his
atomic bonding theory, in "Query 31" of his Opticks, whereby atoms attach to each other by some "force".
Specifically, after acknowledging the various popular theories in vogue at the time, of how atoms were reasoned to
attach to each other, i.e. "hooked atoms", "glued together by rest", or "stuck together by conspiring motions",
Newton states that he would rather infer from their cohesion, that "particles attract one another by some force, which
in immediate contact is exceedingly strong, at small distances performs the chemical operations, and reaches not far
from the particles with any sensible effect."
In 1819, on the heels of the invention of the voltaic pile, Jns Jakob Berzelius developed a theory of chemical
combination stressing the electronegative and electropositive character of the combining atoms. By the mid 19th
century, Edward Frankland, F.A. Kekul, A.S. Couper, A.M. Butlerov, and Hermann Kolbe, building on the theory
of radicals, developed the theory of valency, originally called "combining power", in which compounds were joined
owing to an attraction of positive and negative poles. In 1916, chemist Gilbert N. Lewis developed the concept of the
electron-pair bond, in which two atoms may share one to six electrons, thus forming the single electron bond, a
single bond, a double bond, or a triple bond; in Lewis's own words, "An electron may form a part of the shell of two
different atoms and cannot be said to belong to either one exclusively."[1]
That same year, Walther Kossel put forward a theory similar to Lewis' only his model assumed complete transfers of
electrons between atoms, and was thus a model of ionic bonds. Both Lewis and Kossel structured their bonding
models on that of Abegg's rule (1904).
In 1927, the first mathematically complete quantum description of a simple chemical bond, i.e. that produced by one
electron in the hydrogen molecular ion, H2+, was derived by the Danish physicist Oyvind Burrau.[2] This work
showed that the quantum approach to chemical bonds could be fundamentally and quantitatively correct, but the
mathematical methods used could not be extended to molecules containing more than one electron. A more practical,
albeit less quantitative, approach was put forward in the same year by Walter Heitler and Fritz London. The
Heitler-London method forms the basis of what is now called valence bond theory. In 1929, the linear combination
of atomic orbitals molecular orbital method (LCAO) approximation was introduced by Sir John Lennard-Jones, who
also suggested methods to derive electronic structures of molecules of F2 (fluorine) and O2 (oxygen) molecules, from
basic quantum principles. This molecular orbital theory represented a covalent bond as an orbital formed by
combining the quantum mechanical Schrdinger atomic orbitals which had been hypothesized for electrons in single
atoms. The equations for bonding electrons in multi-electron atoms could not be solved to mathematical perfection
(i.e., analytically), but approximations for them still gave many good qualitative predictions and results. Most
quantitative calculations in modern quantum chemistry use either valence bond or molecular orbital theory as a
starting point, although a third approach, Density Functional Theory, has become increasingly popular in recent
years.
In 1935, H. H. James and A. S. Coolidge carried out a calculation on the dihydrogen molecule that, unlike all
previous calculation which used functions only of the distance of the electron from the atomic nucleus, used
functions which also explicitly added the distance between the two electrons.[3] With up to 13 adjustable parameters
they obtained a result very close to the experimental result for the dissociation energy. Later extensions have used up
to 54 parameters and give excellent agreement with experiment. This calculation convinced the scientific community
that quantum theory could give agreement with experiment. However this approach has none of the physical pictures
of the valence bond and molecular orbital theories and is difficult to extend to larger molecules.
262
Chemical bond
263
Chemical bond
264
a particular set of atomic orbitals, we reach what is called the full configuration interaction wave function. If we take
the simple molecular orbital description of the ground state and combine that function with the functions describing
all possible excited states using unoccupied orbitals arising from the same set of atomic orbitals, we also reach the
full configuration interaction wavefunction. It can be then seen that the simple molecular orbital approach gives too
much weight to the ionic structures, while the simple valence bond approach gives too little. This can also be
described as saying that the molecular orbital approach is too delocalised, while the valence bond approach is too
localised.
The two approaches are now regarded as complementary, each providing its own insights into the problem of
chemical bonding. Modern calculations in quantum chemistry usually start from (but ultimately go far beyond) a
molecular orbital rather than a valence bond approach, not because of any intrinsic superiority in the former but
rather because the MO approach is more readily adapted to numerical computations. However better valence bond
programs are now available.
Length
(pm)
Energy
(kJ/mol)
H Hydrogen
HH
74
436
HO
96
366
HF
92
568
HCl
127
432
C Carbon
CH
109
413
CC
154
348
C=C
134
614
CC
120
839
CN
147
308
Chemical bond
265
CO
143
360
CF
134
488
CCl
177
330
N Nitrogen
NH
101
391
NN
145
170
NN
110
945
O Oxygen
OO
148
145
O=O
121
498
142
158
ClCl
199
243
BrH
141
366
BrBr
228
193
IH
161
298
II
267
151
Strong chemical bonds are the intramolecular forces which hold atoms together in molecules. A strong chemical
bond is formed from the transfer or sharing of electrons between atomic centers and relies on the electrostatic
attraction between the protons in nuclei and the electrons in the orbitals. Although these bonds typically involve the
transfer of integer numbers of electrons (this is the bond order, which respresents one transferred electron or two
shared electrons), some systems can have intermediate numbers of bonds. An example of this is the organic molecule
benzene, where the bond order is 1.5 for each carbon atom, meaning that it has 1.5 bonds (shares three electrons)
with each one of its two neighbors.
The types of strong bond differ due to the difference in electronegativity of the constituent elements. A large
difference in electronegativity leads to more polar (ionic) character in the bond.
Covalent bond
Covalent bonding is a common type of bonding, in which the electronegativity difference between the bonded atoms
is small or nonexistent. Bonds within most [organic compound]s are described as covalent. See [sigma bond]s and pi
bonds for LCAO-description of such bonding.
A polar covalent bond is a covalent bond with a significant ionic character. This means that the electrons are closer
to one of the atoms than the other, creating an imbalance of charge. They occur as a bond between two atoms with
moderately different electronegativities, and give rise to dipole-dipole interactions. The electronegativity of these
bonds is 0.3 to 1.7 .
A coordinate covalent bond is one where both bonding electrons are from one of the atoms involved in the bond.
These bonds give rise to Lewis acids and bases. The electrons are shared roughly equally between the atoms in
contrast to ionic bonding. Such bonding occurs in molecules such as the ammonium ion (NH4+) and are shown by an
arrow pointing to the Lewis acid. Also known as non-polar covalent bond, the electronegativity of these bonds range
from 0 to 0.3.
Molecules which are formed primarily from non-polar covalent bonds are often immiscible in water or other polar
solvents, but much more soluble in non-polar solvents such as hexane.
Chemical bond
Ionic bond
Ionic bonding is a type of electrostatic interaction between atoms which have a large electronegativity difference.
There is no precise value that distinguishes ionic from covalent bonding, but a difference of electronegativity of over
1.7 is likely to be ionic, and a difference of less than 1.7 is likely to be covalent.[5] Ionic bonding leads to separate
positive and negative ions. Ionic charges are commonly between 3e to +3e. Ionic bonding commonly occurs in
metal salts such as sodium chloride (table salt). A typical feature of ionic bonds is that the species form into ionic
crystals, in which no ion is specifically paired with any single other ion, in a specific directional bond. Rather, each
species of ion is surrounded by ions of the opposite charge, and the spacing between it and each of the oppositely
charged ions near it, is the same for all surrounding atoms of the same type. It is thus no longer possible to associate
an ion with any specific other single ionized atom near it. This is a situation unlike that in covalent crystals, where
covalent bonds between specific atoms are still discernable from the shorter distances between them, as measured by
with such techniques as X-ray diffraction.
Ionic crystals may contain a mixture of covalent and ionic species, as for example salts of complex acids, such as
sodium cyanide, NaCN. Many minerals are of this type. X-ray diffration shows that in NaCN, for example, the bonds
between sodium cations (Na+) and the cyanide anions (CN-) are ionic, with no sodium ion associated with any
particular cyanide. However, the bonds between C and N atoms in cyanide are of the covalent type, making each of
the carbon and nitrogen associated with just one of its opposite type, to which it is physically much closer than it is
to other carbons or nitrogens in a sodium cyanide crystal.
When such crystals are melted into liquids, the ionic bonds are broken first because they are non-directional and
allow the charged species to move freely. Similarly, when such salts dissolve into water, the ionic bonds are typically
broken by the interaction with water, but the covalent bonds continue to hold. For example, in solution, the cyanide
ions, still bound together as single CN- ions, move independently through the solution, as do sodium ions, as Na+. In
water, charged ions move apart because each of them are more strongly attracted to a number of water molecules,
than to each other. The attraction between ions and water molecules in such solutions is due to a type of weak
dipole-dipole type chemical bond. In melted ionic compounds, the ions continue to be attracted to each other, but not
in any ordered or crystalline way.
266
Chemical bond
Bent bonds
Bent bonds, also known as banana bonds, are bonds in strained or otherwise sterically hindered molecules whose
binding orbitals are forced into a banana-like form. Bent bonds are often more susceptible to reactions than ordinary
bonds.
Aromatic bond
In organic chemistry, certain configurations of electrons and orbitals infer extra stability to a molecule. This occurs
when orbitals overlap and combine with others on different atomic centres, forming a long range bond. For a
molecule to be aromatic, it must obey Hckel's rule, where the number of electrons fit the formula 4n + 2, where n
is an integer. The bonds involved in the aromaticity are all planar.
In benzene, the prototypical aromatic compound, 18 (n = 4) bonding electrons bind 6 carbon atoms together to form
a planar ring structure. The bond "order" (average number of bonds) between the different carbon atoms may be said
to be (18/6)/2=1.5, but in this case the bonds are all identical from the chemical point of view. They may sometimes
be written as single bonds alternating with double bonds, but the view of all ring bonds as being equivalently about
1.5 bonds in strength, is much closer to truth.
In the case of heterocyclic aromatics and substituted benzenes, the electronegativity differences between different
parts of the ring may dominate the chemical behaviour of aromatic ring bonds, which otherwise are equivalent.
Metallic bond
In a metallic bond, bonding electrons are delocalized over a lattice of atoms. By contrast, in ionic compounds, the
locations of the binding electrons and their charges are static. The freely-moving or delocalization of bonding
electrons leads to classical metallic properties such as shininess (surface light reflectivity), electrical and thermal
conductivity, ductility, and high tensile strength.
Intermolecular bonding
There are four basic types of bonds that can be formed between two or more (otherwise non-associated) molecules,
ions or atoms. Intermolecular forces cause molecules to be attracted or repulsed by each other. Often, these define
some of the physical characteristics (such as the melting point) of a substance.
A large difference in electronegativity between two bonded atoms will cause a permanent charge separation, or
dipole, in a molecule or ion. Two or more molecules or ions with permanent dipoles can interact in dipole-dipole
interactions. The bonding electrons in a molecule or ion will, on average, be closer to the more electronegative
atom more frequently than the less electronegative one, giving rise to partial charges on each atom, and causing
electrostatic forces between molecules or ions.
267
Chemical bond
A hydrogen bond is effectively a strong example of a permanent dipole. The large difference in
electronegativities between hydrogen and any of fluorine, nitrogen and oxygen, coupled with their lone pairs of
electrons cause strong electrostatic forces between molecules. Hydrogen bonds are responsible for the high
boiling points of water and ammonia with respect to their heavier analogues.
The London dispersion force arises due to instantaneous dipoles in neighbouring atoms. As the negative charge
of the electron is not uniform around the whole atom, there is always a charge imbalance. This small charge will
induce a corresponding dipole in a nearby molecule; causing an attraction between the two. The electron then
moves to another part of the electron cloud and the attraction is broken.
A cationpi interaction occurs between the electron density of pi bonds above and below an aromatic ring and a
cation.
References
[1] Lewis, Gilbert N. (1916). "The Atom and the Molecule". Journal of the American Chemical Society 38: 772.
[2] Laidler, K. J. (1993). The World of Physical Chemistry. Oxford University Press. p.347.
[3] James, H. H.; A. S. Coolidge (1933). "The Ground State of the Hydrogen Molecule". Journal of Chemical Physics (American Institute of
Physics) 1 (12): 825835. doi:10.1063/1.1749252.
[4] http:/ / www. science. uwaterloo. ca/ ~cchieh/ cact/ c120/ bondel. html
[5] Atkins, Peter; Loretta Jones (1997). Chemistry: Molecules, Matter and Change. New York: W. H. Freeman & Co.. pp.294295.
ISBN0-7167-3107-X.
[6] Weinhold, F.; Landis, C. (2005). Valency and bonding. Cambridge. pp.96100. ISBN0521831288.
[7] Pauling, L. The Nature of the Chemical Bond. Cornell University Press, 1960.
External links
W. Locke (1997). Introduction to Molecular Orbital Theory (http://www.ch.ic.ac.uk/vchemlib/course/
mo_theory/main.html). Retrieved May 18, 2005.
Carl R. Nave (2005). HyperPhysics (http://hyperphysics.phy-astr.gsu.edu/hbase/chemical/bond.html).
Retrieved May 18, 2005.
Linus Pauling and the Nature of the Chemical Bond: A Documentary History (http://osulibrary.oregonstate.
edu/specialcollections/coll/pauling/bond/index.html). Retrieved February 29, 2008.
268
269
Chemical reactions
Chemical reaction
A chemical reaction is a process that leads to the transformation of
one set of chemical substances to another.[1] Chemical reactions can be
either spontaneous, requiring no input of energy, or non-spontaneous,
typically following the input of some type of energy, such as heat, light
or electricity. Classically, chemical reactions encompass changes that
strictly involve the motion of electrons in the forming and breaking of
chemical bonds, although the general concept of a chemical reaction,
in particular the notion of a chemical equation, is applicable to
transformations of elementary particles (such as illustrated by
Feynman diagrams), as well as nuclear reactions.
The substance (or substances) initially involved in a chemical reaction
are called reactants or reagents. Chemical reactions are usually
characterized by a chemical change, and they yield one or more
A thermite reaction using iron(III) oxide. The
sparks flying outwards are globules of molten
products, which usually have properties different from the reactants.
iron trailing smoke in their wake.
Reactions often consist of a sequence of individual sub-steps, the
so-called elementary reactions, and the information on the precise
course of action is part of the reaction mechanism. Chemical reactions are described with chemical equations, which
graphically present the starting materials, end products, and sometimes intermediate products and reaction
conditions.
Different chemical reactions are used in combination in chemical synthesis in order to obtain a desired product. In
biochemistry, series of chemical reactions catalyzed by enzymes form metabolic pathways, by which syntheses and
decompositions impossible under ordinary conditions are performed within a cell.
Chemical reaction
History
Chemical reactions such as combustion in the fire, fermentation and
the reduction of ores to metals were known since antiquity. Initial
theories of transformation of materials were developed by Greek
philosophers, such as the Four-Element Theory of Empedocles stating
that any substance is composed of the four basic elements fire, water,
air and earth. In the Middle Ages, chemical transformations were
studied by Alchemists. They attempted, in particular, to convert lead
into gold, for which purpose they used reactions of lead and
lead-copper alloys with sulfur.[2]
The production of chemical substances that do not normally occur in
nature has long been tried, such as the synthesis of sulfuric and nitric
acids attributed to the controversial alchemist Jbir ibn Hayyn. The
process involved heating of sulfate and nitrate minerals such as copper
sulfate, alum and saltpeter. In the 17th century, Johann Rudolph
Glauber produced hydrochloric acid and sodium sulfate by reacting
sulfuric acid and sodium chloride. With the development of the lead
Antoine Lavoisier developed the theory of
chamber process in 1746 and the Leblanc process, allowing large-scale
combustion
as a chemical reaction with oxygen
production of sulfuric acid and sodium carbonate, respectively,
chemical reactions became implemented into the industry. Further
optimization of sulfuric acid technology resulted in the contact process in 1880s,[3] and the Haber process was
developed in 19091910 for ammonia synthesis.[4]
From the 16th century, researchers including Jan Baptist van Helmont, Robert Boyle and Isaac Newton tried to
establish theories of the experimentally observed chemical transformations. The phlogiston theory was proposed in
1667 by Johann Joachim Becher. It postulated the existence of a fire-like element called "phlogiston", which was
contained within combustible bodies and released during combustion. This proved to be false in 1785 by Antoine
Lavoisier who found the correct explanation of the combustion as reaction with oxygen from the air.[5]
Joseph Louis Gay-Lussac recognized in 1808 that gases always react in a certain relationship with each other. Based
on this idea and the atomic theory of John Dalton, Joseph Proust had developed the law of definite proportions,
which later resulted in the concepts of stoichiometry and chemical equations.[6]
Regarding the organic chemistry, it was long believed that compounds obtained from living organisms were too
complex to be obtained synthetically. According to the concept of vitalism, organic matter was endowed with a "vital
force" and distinguished from inorganic materials. This separation was ended however by the synthesis of urea from
inorganic precursors by Friedrich Whler in 1828. Other chemists who brought major contributions to organic
chemistry include Alexander William Williamson with his synthesis of ethers and Christopher Kelk Ingold, who,
among many discoveries, established the mechanisms of substitution reactions.
Equations
Chemical equations are used to graphically illustrate chemical reactions. They consist of chemical or structural
formulas of the reactants on the left and those of the products on the right. They are separated by an arrow ()
which indicates the direction and type of the reaction. The tip of the arrow points in the direction in which the
reaction proceeds. A double arrow (
) pointing in opposite directions is used for equilibrium reactions. Equations
should be balanced according to the stoichiometry, the number of atoms of each species should be the same on both
sides of the equation. This is achieved by scaling the number of involved molecules (A, B, C and D in a schematic
example below) by the appropriate integers a, b, c and d.[7]
270
Chemical reaction
271
More elaborate reactions are represented by reaction schemes, which in addition to starting materials and products
show important intermediates or transition states. Also, some relatively minor additions to the reaction can be
indicated above the reaction arrow; examples of such additions are water, heat, illumination, a catalyst, etc.
Similarly, some minor products can be placed below the arrow, often with a minus sign.
Retrosynthetic analysis can be applied to design a complex synthesis reaction. Here the analysis starts from the
products, for example by splitting selected chemical bonds, to arrive at plausible initial reagents. A special arrow
() is used in retro reactions.[8]
Elementary reactions
The elementary reaction is the smallest division into which a chemical reaction can be decomposed to, it has no
intermediate products.[9] Most experimentally observed reactions are built up from many elementary reactions that
occur in parallel or sequentially. The actual sequence of the individual elementary reactions is known as reaction
mechanism. An elementary reaction involves a few molecules, usually one or two, because of the low probability for
several molecules to meet at a certain time.[10]
The most important elementary reactions are
unimolecular and bimolecular reactions.
Only one molecule is involved in a
unimolecular reaction; it is transformed by
an isomerization or a dissociation in one or
more other molecules. Such reaction
requires addition of energy in the form of
heat or light. A typical example of a
unimolecular reaction is the cistrans
isomerization, in which the cis-form of a
compound converts to the trans-form or vice versa.[11]
In a typical dissociation reaction, a bond in a molecule splits resulting in two molecular fragments. The splitting can
be homolytic or heterolytic. In the first case, the bond is divided so that each product retains an electron and becomes
a neutral radical. In the second case, both electrons of the chemical bond remain with one of the products, resulting
in charged ions. Dissociation plays an important role in triggering chain reactions, such as hydrogenoxygen or
polymerization reactions.
For bimolecular reactions, two molecules collide and react with each other. Their merger is called chemical synthesis
or an addition reaction.
Another possibility is that only a portion of one molecule is transferred to the other molecule. This type of reaction
occurs, for example, in redox and acid-base reactions. In redox reactions, the transferred particle is an electron,
Chemical reaction
whereas in acid-base reactions it is a proton. This type of reaction is also called metathesis.
for example
NaCl(aq) + AgNO3(aq) NaNO3(aq) + AgCl(s)
Chemical equilibrium
Most chemical reactions are reversible, that is they can and do run in both directions. The forward and reverse
reactions are competing with each other and differ in reaction rates. These rates depend on the concentration and
therefore change with time of the reaction: the reverse rate gradually increases and becomes equal to the rate of the
forward reaction, establishing the so-called chemical equilibrium. The time to reach equilibrium depends on such
parameters as temperature, pressure and the materials involved, and is determined by the minimum free energy. In
equilibrium, the Gibbs free energy must be zero. The pressure dependence can be explained with the Le Chatelier's
principle. For example, an increase in pressure due to decreasing volume causes the reaction to shift to the side with
the fewer moles of gas.[12]
The reaction yield stabilized at equilibrium, but can be increased by removing the product from the reaction mixture
or increasing temperature or pressure. Change in the initial concentrations of the substances does not affect the
equilibrium.
Thermodynamics
Chemical reactions are determined by the laws of thermodynamics. Reactions can proceed by themselves if they are
exergonic, that is if they release energy. The associated free energy of the reaction is composed of two different
thermodynamic quantities, enthalpy and entropy:[13]
Reactions can be exothermic, where H is negative and energy is released. Typical examples of exothermic
reactions are precipitation and crystallization, in which ordered solids are formed from disordered gaseous or liquid
phases. In contrast, in endothermic reactions, heat is consumed from the environment. This can occur by increasing
the entropy of the system, often through the formation of gaseous reaction products, which have high entropy. Since
the entropy increases with temperature, many endothermic reactions preferably take place at high temperatures. On
the contrary, many exothermic reactions such as crystallization occur at low temperatures. Changes in temperature
can sometimes reverse the direction of a reaction, as in the Boudouard reaction:
This reaction between carbon dioxide and carbon to form carbon monoxide is endothermic at temperatures above
approximately 800 C and is exothermic below this temperature.[14]
Reactions can also be characterized with the internal energy which takes into account changes in the entropy, volume
and chemical potential. The latter depends, among other things, on the activities of the involved substances.[15]
U: internal energy, S: entropy, p: pressure, : chemical potential, n: number of molecules, d: small change sign
272
Chemical reaction
Kinetics
The speed at which a reactions takes place is studied by reaction kinetics. The rate depends on various parameters,
such as:
Reactant concentrations, which usually make the reaction happen at a faster rate if raised through increased
collisions per unit time. Some reactions, however, have rates that are independent of reactant concentrations.
These are called zero order reactions.
Surface area available for contact between the reactants, in particular solid ones in heterogeneous systems. Larger
surface areas lead to higher reaction rates.
Pressure increasing the pressure decreases the volume between molecules and therefore increases the frequency
of collisions between the molecules.
Activation energy, which is defined as the amount of energy required to make the reaction start and carry on
spontaneously. Higher activation energy implies that the reactants need more energy to start than a reaction with a
lower activation energy.
Temperature, which hastens reactions if raised, since higher temperature increases the energy of the molecules,
creating more collisions per unit time,
The presence or absence of a catalyst. Catalysts are substances which change the pathway (mechanism) of a
reaction which in turn increases the speed of a reaction by lowering the activation energy needed for the reaction
to take place. A catalyst is not destroyed or changed during a reaction, so it can be used again.
For some reactions, the presence of electromagnetic radiation, most notably ultraviolet light, is needed to promote
the breaking of bonds to start the reaction. This is particularly true for reactions involving radicals.
Several theories allow calculating the reaction rates at the molecular level. This field is referred to as reaction
dynamics. The rate v of a first-order reaction, which could be disintegration of a substance A, is given by:
Here k is first-order rate constant having dimension 1/time, [A](t) is concentration at a time t and [A]0 is the initial
concentration. The rate of a first-order reaction depends only on the concentration and the properties of the involved
substance, and the reaction itself can be described with the characteristic half-life. More than one time constant is
needed when describing reactions of higher order. The temperature dependence of the rate constant usually follows
the Arrhenius equation:
where Ea is the activation energy and kB is the Boltzmann constant. One of the simplest models of reaction rate is the
collision theory. More realistic models are tailored to a specific problem and include the transition state theory, the
calculation of the potential energy surface, the Marcus theory and the RiceRamspergerKasselMarcus (RRKM)
theory.[16]
273
Chemical reaction
274
Reaction types
Four basic types
Synthesis
In a synthesis reaction, two or more simple substances combine to form a more complex substance. Two or more
reactants yielding one product is another way to identify a synthesis reaction. For example, simple hydrogen gas
combined with simple oxygen gas can produce a more complex substance, such as water.[17]
Decomposition
A decomposition reaction is the opposite of a synthesis reaction, where a more complex substance breaks down into
its more simple parts.[17] [18]
Single replacement
In a single replacement reaction, a single uncombined element replaces another in a compound.[17]
Double replacement
In a double replacement reaction, parts of two compounds switch places to form two new compounds.[17] This is
when the anions and cations of two different molecules switch places, forming two entirely different compounds.[18]
These reactions are in the general form:
AB + CD AD + CB
An example of a double displacement reaction is the reaction of lead(II) nitrate with potassium iodide to form
lead(II) iodide and potassium nitrate:
Pb(NO3)2 + 2 KI PbI2 + 2 KNO3
Which of the involved reactants would be reducing or oxidizing agent can be predicted from the electronegativity of
their elements. Elements with low electronegativity, such as most metals, easily donate electrons and oxidize they
are reducing agents. On the contrary, many ions with high oxidation numbers, such as H2O2, MnO, CrO3, Cr2O,
OsO4) can gain one or two extra electrons and are strong oxidizing agents.
Chemical reaction
275
The number of electrons donated or accepted in a redox reaction can be predicted from electron configuration of the
reactant element. Elements are trying to reach the low-energy noble gas configuration, and therefore alkali metals
and halogens will donate and accept one electron, respectively, and the noble gases themselves are chemically
inactive.[21]
An important class of redox reactions are the electrochemical reactions, where the electrons from the power supply
are used as a reducing agent. These reactions are particularly important for the production of chemical elements,
such as chlorine[22] or aluminium. The reverse process in which electrons are released in redox reactions and can be
used as electrical energy is possible and is used in the batteries.
Complexation
In complexation reactions, several ligands react with a metal atom to form a
coordination complex. This is achieved by providing lone pairs of the
ligand into empty orbitals of the metal atom and forming dipolar bonds.
The ligands are Lewis bases, they can be both ions and neutral molecules,
such as carbon monoxide, ammonia or water. The number of ligands that
react with a central metal atom can be found using the 18-electron rule,
saying that the valence shells of a transition metal will collectively
accommodate 18 electrons, whereas the symmetry of the resulting complex
can be predicted with the crystal field theory and ligand field theory.
Complexation reactions also include ligand exchange, in which one or more
ligands are replaced by another, and redox processes which change the
oxidation state of the central metal atom.[23]
Acid-base reactions
Acid-base reactions involve transfer of protons from one molecule (acid) to another (base). Here, acids act as proton
donors and bases as acceptors.
Acid-base reaction, HA: acid, B: Base, A: conjugated base, HB+: conjugated acid
The associated proton transfer results in the so-called conjugate acid and conjugate base.[24] The reverse reaction is
possible, and thus the acid/base and conjugated base/acid are always in equilibrium. The equilibrium is determined
by the acid and base dissociation constants (Ka and Kb) of the involved substances. A special case of the acid-base
reaction is the neutralization where an acid and a base, taken at exactly same amounts, form a neutral salt.
Acid-base reactions can have different definitions depending on the acid-base concept employed. Some of the most
common are:
Arrhenius definition: Acids dissociate in water releasing H3O+ ions; bases dissociate in water releasing OH ions.
Brnsted-Lowry definition: Acids are proton (H+) donors, bases are proton acceptors; this includes the Arrhenius
definition.
Lewis definition: Acids are electron-pair acceptors, bases are electron-pair donors; this includes the
Brnsted-Lowry definition.
Chemical reaction
276
Precipitation
Precipitation is the formation of a solid in a solution or inside another
solid during a chemical reaction. It usually takes place when the
concentration of dissolved ions exceeds the solubility limit[25] and
forms an insoluble salt. This process can be assisted by adding a
precipitating agent or by removal of the solvent. Rapid precipitation
results in an amorphous or microcrystalline residue and slow process
can yield single crystals. The latter can also be obtained by
recrystallization from microcrystalline salts.[26]
Solid-state reactions
Reactions can take place between two solids. However, because of the
Precipitation
relatively small diffusion rates in solids, the corresponding chemical
reactions are very slow. They are accelerated by increasing the reaction temperature and finely dividing the reactant
to increase the contacting surface area.[27]
Photochemical reactions
In photochemical reactions, atoms and molecules absorb energy
(photons) of the illumination light and convert into an excited state.
They can then release this energy by breaking chemical bonds, thereby
producing radicals. Photochemical reactions include hydrogenoxygen
reactions, radical polymerization, chain reactions and rearrangement
reactions.[28]
Chemical reaction
277
Catalysis
In catalysis, the reaction does not proceed directly, but through a third
substance known as catalyst. Unlike other reagents that participate in
the chemical reaction, a catalyst is not consumed by the reaction itself;
however, it can be inhibited, deactivated or destroyed by secondary
processes. Catalysts can be used in a different phase (heterogeneous) or
in the same phase (homogenous) as the reactants. In heterogeneous
catalysis, typical secondary processes include coking where the
catalyst becomes covered by polymeric side products. Additionally,
heterogeneous catalysts can dissolve into the solution in a solidliquid
system or evaporate in a solidgas system. Catalysts can only speed up
the reaction chemicals that slow down the reaction are called
inhibitors.[30] [31] Substances that increase the activity of catalysts are
called promoters, and substances that deactivate catalysts are called
catalytic poisons. With a catalyst, a reaction which is kinetically
inhibited by a high activation energy can take place in circumvention
of this activation energy.
Heterogeneous catalysts are usually solids, powdered in order to
maximize their surface area. Of particular importance in heterogeneous
catalysis are the platinum group metals and other transition metals,
which are used in hydrogenations, catalytic reforming and in the
synthesis of commodity chemicals such as nitric acid and ammonia.
Acids are an example of a homogeneous catalyst, they increase the
nucleophilicity of carbonyls, allowing a reaction that would not
otherwise proceed with electrophiles. The advantage of homogeneous
catalysts is the ease of mixing them with the reactants, but they may
also be difficult to separate from the products. Therefore,
heterogeneous catalysts are preferred in many industrial processes.[32]
Chemical reaction
278
Substitution
In a substitution reaction, a functional group in a particular chemical compound is replaced by another group.[33]
These reactions can be distinguished by the type of substituting species into a nucleophilic, electrophilic or radical
substitution.
SN1 mechanism
SN2 mechanism
In the first type, a nucleophile, an atom or molecule with an excess of electrons and thus a negative charge or partial
charge, replaces another atom or part of the "substrate" molecule. The electron pair from the nucleophile attacks the
substrate forming a new bond, while the leaving group departs with an electron pair. The nucleophile may be
electrically neutral or negatively charged, whereas the substrate is typically neutral or positively charged. Examples
of nucleophiles are hydroxide ion, alkoxides, amines and halides. This type of reaction is found mainly in aliphatic
hydrocarbons, and rarely in aromatic hydrocarbon. The latter have high electron density and enter nucleophilic
aromatic substitution only with very strong electron withdrawing groups. Nucleophilic substitution can take place by
two different mechanisms, SN1 and SN2. In their names, S stands for substitution, N for nucleophilic, and the
number represents the kinetic order of the reaction, unimolecular or bimolecular.[34]
The three steps of an SN2 reaction. The nucleophile is green and the leaving group is red
The SN1 reaction proceeds in two steps. First, the leaving group is eliminated creating a carbocation. This is
followed by a rapid reaction with the nucleophile.[35]
In the SN2 mechanism, the nucleophile forms a transition state with the attacked molecule, and only then the leaving
group is cleaved. These two mechanisms differ in the stereochemistry of the products. SN1 leads to the
Chemical reaction
279
non-stereospecific addition and does not result in a chiral center, but rather in a set of geometric isomers (cis/trans).
In contrast, a reversal (Walden inversion) of the previously existing stereochemistry is observed in the SN2
mechanism.[36]
Electrophilic substitution is the counterpart of the nucleophilic substitution in that the attacking atom or molecule, an
electrophile, has low electron density and thus a positive charge. Typical electrophiles are the carbon atom of
carbonyl groups, carbocations or sulfur or nitronium cations. This reaction takes place almost exclusively in aromatic
hydrocarbons, where it is called electrophilic aromatic substitution. The electrophile attack results in the so-called
-complex, a transition state in which the aromatic system is abolished. Then, the leaving group, usually a proton, is
split off and the aromaticity is restored. An alternative to aromatic substitution is electrophilic aliphatic substitution.
It is similar to the nucleophilic aliphatic substitution and also has two major types, SE1 and SE2[37]
In the third type of substitution reaction, radical substitution, the attacking particle is a radical.[33] This process
usually takes the form of a chain reaction, for example in the reaction of alkanes with halogens. In the first step, light
or heat disintegrates the halogen-containing molecules producing the radicals. Then the reaction proceeds as an
avalanche until two radicals meet and recombine.[38]
Chemical reaction
280
E1 elimination
E1cb elimination
Chemical reaction
281
Nucleophilic addition of a carbanion or another nucleophile to the double bond of an alpha, beta unsaturated
carbonyl compound can proceed via the Michael reaction, which belongs to the larger class of conjugate additions.
This is one of the most useful methods for the mild formation of C-C bonds.[46] [47] [48]
Some additions which can not be executed with nucleophiles and electrophiles, can be succeeded with free radicals.
As with the free-radical substitution, the radical addition proceeds as a chain reaction, and such reactions are the
basis of the free-radical polymerization.[49]
In a rearrangement reaction, the carbon skeleton of a molecule is rearranged to give a structural isomer of the
original molecule. These include hydride shift reactions such as the Wagner-Meerwein rearrangement, where a
hydrogen, alkyl or aryl group migrates from one carbon to a neighboring carbon. Most rearrangements are associated
with the breaking and formation of new carbon-carbon bonds. Other examples are sigmatropic reaction such as the
Cope rearrangement.[50]
Cyclic rearrangements include cycloadditions and, more generally, pericyclic reactions, wherein two or more double
bond-containing molecules form a cyclic molecule. An important example of cycloaddition reaction is the
DielsAlder reaction (the so-called [4+2] cycloaddition) between a conjugated diene and a substituted alkene to form
a substituted cyclohexene system.[51]
Whether or not a certain cycloaddition would proceed depends on the electronic orbitals of the participating species,
as only orbitals with the same sign of wave function will overlap and interact constructively to form new bonds.
Chemical reaction
282
Cycloaddition is usually assisted by light or heat. These perturbations result in different arrangement of electrons in
the excited state of the involved molecules and therefore in different effects. For example, the [4+2] Diels-Alder
reactions can be assisted by heat whereas the [2+2] cycloaddition is selectively induced by light.[52] Because of the
orbital character, the potential for developing stereoisomeric products upon cycloaddition is limited, as described by
the Woodward-Hoffmann rules.[53]
Biochemical reactions
Biochemical reactions are mainly
controlled by enzymes. These proteins
can specifically catalyze a single
reaction, so that reactions can be
controlled very precisely. The reaction
takes place in the active site, a small
part of the enzyme which is usually
found in a cleft or pocket lined by
amino acid residues, and the rest of the
Illustration of the induced fit model of enzyme activity
enzyme
is
used
mainly
for
stabilization. The catalytic action of enzymes relies on several mechanisms including the molecular shape ("induced
fit"), bond strain, proximity and orientation of molecules relative to the enzyme, proton donation or withdrawal
(acid/base catalysis), electrostatic interactions and many others.[54]
The biochemical reactions that occur in living organisms are collectively known as metabolism. Among the most
important of its mechanisms is the anabolism, in which different DNA and enzyme-controlled processes result in the
production of large molecules such as proteins and carbohydrates from smaller units.[55] Bioenergetics studies the
sources of energy for such reactions. An important energy source is glucose, which can be produced by plants via
photosynthesis or assimilated from food. All organisms use this energy to produce adenosine triphosphate (ATP),
which can then be used to energize other reactions.
Applications
Chemical reactions are central to chemical engineering where they are
used for the synthesis of new compounds from natural raw materials
such as petroleum and mineral ores. It is essential to make the reaction
as efficient as possible, maximizing the yield and minimizing the
amount of reagents, energy inputs and waste. Catalysts are especially
helpful for reducing the energy required for the reaction and increasing
its reaction rate.[56] [57]
Some specific reactions have their niche applications. For example, the
thermite reaction is used to generate light and heat in pyrotechnics and
welding. Although it is less controllable than the more conventional
oxy-fuel welding, arc welding and flash welding, it requires much less
equipment and is still used to mend rails, especially in remote areas.[58]
Chemical reaction
Monitoring
Mechanisms of monitoring chemical reactions depend strongly on the reaction rate. Relatively slow processes can be
analyzed in situ for the concentrations and identities of the individual ingredients. Important tools of real time
analysis are the measurement of pH and analysis of optical absorption (color) and emission spectra. A less accessible
but rather efficient method is introduction of a radioactive isotope into the reaction and monitoring how it changes
over time and where it moves to; this method is often used to analyze redistribution of substances in the human body.
Faster reactions are usually studied with ultrafast laser spectroscopy where utilization of femtosecond lasers allows
short-lived transition states to be monitored at time scaled down to a few femtoseconds.[59]
References
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[2] Weyer, Jost (1973). "Neuere Interpretationsmglichkeiten der Alchemie" (in German). Chemie in unserer Zeit 7 (6): 177.
doi:10.1002/ciuz.19730070604.
[3] Leonard J. Friedman & Samantha J. Friedman The History of the Contact Sulfuric Acid Process (http:/ / www. aiche-cf. org/ Clearwater/
2008/ Paper2/ 8. 2. 7. pdf), Acid Engineering & Consulting, Inc. Boca Raton, Florida
[4] John E. Lesch The German chemical industry in the twentieth century (http:/ / books. google. com/ books?id=VJIztvolC8cC& pg=PA170),
Springer, 2000, ISBN 0792364872 p. 170
[5] Brock, pp. 3455
[6] Brock, pp. 104107
[7] IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006) " chemical reaction
equation (http:/ / goldbook. iupac. org/ C01034. html)".
[8] Corey, E. J. (1988). "Robert Robinson Lecture. Retrosynthetic thinking?essentials and examples". Chemical Society Reviews 17: 111.
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(http:/ / goldbook. iupac. org/ E02035. html)".
[10] Gernot Frenking: Elementarreaktionen. In: Rmpp Chemie-Lexikon, Thieme, 2006
[11] Christophe Dugave Cis-trans isomerization in biochemistry (http:/ / books. google. com/ books?id=udSCHPq5Ii0C& pg=PA56),
Wiley-VCH, 2006 ISBN 3527313044 p. 56
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[13] Atkins, pp. 106108
[14] Wiberg, pp. 810811
[15] Atkins, p. 150
[16] Atkins, p. 963
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1991 ISBN 0120342421 p. 7
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[33] March, Jerry (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (3rd ed.), New York: Wiley,
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[34] S. R. Hartshorn, Aliphatic Nucleophilic Substitution (http:/ / books. google. com/ books?id=bAo4AAAAIAAJ& printsec=frontcover),
Cambridge University Press, London, 1973. ISBN 0-521-09801-7 pp. 1 ff
[35] Leslie C. Bateman, Mervyn G. Church, Edward D. Hughes, Christopher K. Ingold and Nazeer Ahmed Taher (1940). "188. Mechanism of
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[36] Brckner, pp. 6377
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[38] Brckner, p. 16
[39] Brckner, p. 192
[40] Brckner, p. 183
[41] Brckner, p. 172
[42] Wiberg, pp. 950, 1602
[43] IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006) " Markownikoff rule
(http:/ / goldbook. iupac. org/ M03707. html)".
[44] Brckner, p. 125
[45] Hans Peter Latscha, Uli Kazmaier, Helmut Alfons Klein Organische Chemie: Chemie-basiswissen II, Vol. 2. 6th edition, Springer, 2008,
ISBN 978-3-5407-7106-7, p. 273
[46] . 2004. doi:10.1002/0471264180.
[47] Ian Hunt. "Chapter 18: Enols and Enolates The Michael Addition reaction" (http:/ / www. chem. ucalgary. ca/ courses/ 351/ Carey5th/
Ch18/ ch18-4-3. html). University of Calgary. .
[48] Brckner, p. 580
[49] Manfred Lechner, Klaus Gehrke, Eckhard Nordmeier Macromolecular Chemistry 3rd Edition, Birkhauser, Basel 2003, ISBN
3-7643-6952-3, pp. 5365
[50] Marye Anne Fox, James K. Whitesell Organic chemistry (http:/ / books. google. com/ books?id=xx_uIP5LgO8C& pg=PA699), 2004, ISBN
0763721972 p. 699
[51] Diels, Otto; Alder, Kurt (1928). "Synthesen in der hydroaromatischen Reihe". Justus Liebig's Annalen der Chemie 460: 98.
doi:10.1002/jlac.19284600106.
[52] Brckner, pp. 637647
[53] Woodward, R. B.; Hoffmann, Roald (1965). Journal of the American Chemical Society 87 (2): 395. doi:10.1021/ja01080a054.
[54] Peter Karlson , Detlef Doenecke, Jan Koolman, Georg Fuchs, Wolfgang Gerok. Karlson Biochemistry and Pathobiochemistry, 16th edition,
Georg Thieme, 2005, ISBN 978-3-1335-7815-8, pp. 5556
[55] IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006) " anabolism (http:/ /
goldbook. iupac. org/ A00314. html)".
[56] Gerhard Emig, Elias Klemm. Technical Chemistry. 5th edition, Springer, 2005, ISBN 978-3-5402-3452-4, pp. 3334
[57] Trost, B. (1991). "The atom economya search for synthetic efficiency". Science 254 (5037): 1471. doi:10.1126/science.1962206.
PMID1962206.
[58] John J. McKetta, Guy E Weismantel Encyclopedia of Chemical Processing and Design: Volume 67 Water and Wastewater Treatment:
Protective Coating Systems to Zeolite, Volume 67 (http:/ / books. google. com/ books?id=MfjDlUe8Kc0C& pg=PA109), CRC Press, 1999
ISBN 0824726189, p. 109
[59] Atkins, p. 987
284
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Bibliography
Atkins, Peter W. and Julio de Paula Physical Chemistry, 4th Edition, Wiley-VCH, Weinheim 2006, ISBN
978-3-527-31546-8
Brock, William H. Viewegs Geschichte der Chemie (http://books.google.com/books?id=AJ-c8py7t6gC&
pg=PA459). Vieweg, Braunschweig 1997, ISBN 3-540-67033-5.
Brckner, Reinhard Reaktionsmechanismen. 3rd ed., Spektrum Akademischer Verlag, Mnchen 2004, ISBN
3-8274-1579-9
Wiberg, Egon, Wiberg, Nils and Holleman, Arnold Frederick Inorganic chemistry (http://books.google.com/
books?id=Mtth5g59dEIC&pg=PA287), Academic Press, 2001 ISBN 0123526515
Chemical law
Chemical laws are those laws of nature relevant to chemistry. The most fundamental concept in chemistry is the law
of conservation of mass, which states that there is no detectable change in the quantity of matter during an ordinary
chemical reaction. Modern physics shows that it is actually energy that is conserved, and that energy and mass are
related; a concept which becomes important in nuclear chemistry. Conservation of energy leads to the important
concepts of equilibrium, thermodynamics, and kinetics.
Additional laws of chemistry elaborate on the law of conservation of mass. Joseph Proust's law of definite
composition says that pure chemicals are composed of elements in a definite formulation; we now know that the
structural arrangement of these elements is also important.
Dalton's law of multiple proportions says that these chemicals will present themselves in proportions that are small
whole numbers (i.e. 1:2 O:H in water); although in many systems (notably biomacromolecules and minerals) the
ratios tend to require large numbers, and are frequently represented as a fraction. Such compounds are known as
non-stoichiometric compounds
More modern laws of chemistry define the relationship between energy and transformations.
In equilibrium, molecules exist in mixture defined by the transformations possible on the timescale of the
equilibrium, and are in a ratio defined by the intrinsic energy of the moleculesthe lower the intrinsic energy, the
more abundant the molecule.
Transforming one structure to another requires the input of energy to cross an energy barrier; this can come from
the intrinsic energy of the molecules themselves, or from an external source which will generally accelerate
transformations. The higher the energy barrier, the slower the transformation occurs.
There is a hypothetical intermediate, or transition structure, that corresponds to the structure at the top of the
energy barrier. The Hammond-Leffler Postulate states that this structure looks most similar to the product or
starting material which has intrinsic energy closest to that of the energy barrier. Stabilizing this hypothetical
intermediate through chemical interaction is one way to achieve catalysis.
All chemical processes are reversible (law of microscopic reversibility) although some processes have such an
energy bias, they are essentially irreversible.
285
Solution
286
Solution
In chemistry, a solution is a homogeneous mixture composed of only
one phase. In such a mixture, a solute is dissolved in another
substance, known as a solvent. The solvent does the dissolving.
Types of solutions
Homogeneous means that the components of the mixture form a single
phase. The properties of the mixture (concentration, temperature,
density, etc) can be uniformly distributed through the volume but only
in absence of diffusion phenomena or after their completion. Usually,
the substance present in the greatest amount is considered the solvent.
Solvents can be gases, liquids, or solids. One or more components
present in the solution other than the solvent are called solutes. The
solution has the same physical state as the solvent.
Gas
If the solvent is a gas, only gases are dissolved under any given set of
conditions. An example of a gaseous solution is air (oxygen and other
gases dissolved in nitrogen). Since interactions between molecules play
almost no role, dilute gases form rather trivial solutions. In part of the
literature, they are not even classified as solutions, but addressed as
mixtures.
Liquid
If the solvent is a liquid, then gases, liquids, and solids can be dissolved. Examples are:
Gas in liquid:
Oxygen in water.
Carbon dioxide in water is a less simple example, because the solution is accompanied by a chemical reaction
(formation of ions). Note also that the visible bubbles in carbonated water are not the dissolved gas, but only
an effervescence of carbon dioxide that has come out of solution; the dissolved gas itself is not visible since it
is dissolved on a molecular level.
Liquid in liquid:
The mixing of two or more substances of the same chemistry but different concentrations to form a
constant.(Homogenization of solutions)
Alcoholic beverages are basically solutions of ethanol in water.
Solid in liquid:
Sucrose (table sugar) in water
Sodium chloride or any other salt in water forms an electrolyte: When dissolving, salt dissociates into ions.
Counterexamples are provided by liquid mixtures that are not homogeneous: colloids, suspensions, emulsions are not
considered solutions.
Body fluids are examples for complex liquid solutions, containing many different solutes. They are electrolytes since
they contain solute ions (e.g. potassium and sodium). Furthermore, they contain solute molecules like sugar and urea.
Solution
Oxygen and carbon dioxide are also essential components of blood chemistry, where significant changes in their
concentrations can be a sign of illness or injury.
Solid
If the solvent is a solid, then gases, liquids, and solids can be dissolved.
Gas in solid:
Hydrogen dissolves rather well in metals, especially in palladium; this is studied as a means of hydrogen
storage.
Liquid in solid:
mercury in gold, forming an amalgam
Hexane in paraffin wax
Solid in solid:
Steel, basically a solution of carbon atoms in a crystalline matrix of iron atoms.
Alloys like bronze and many others.
Polymers containing plasticizers.
Solubility
The ability of one compound to dissolve in another compound is called solubility. When a liquid is able to
completely dissolve in another liquid the two liquids are miscible. Two substances that can never mix to form a
solution are called immiscible.
All solutions have a positive entropy of mixing. The interactions between different molecules or ions may be
energetically favored or not. If interactions are unfavorable, then the free energy decreases with increasing solute
concentration. At some point the energy loss outweighs the entropy gain, and no more solute particles can be
dissolved; the solution is said to be saturated. However, the point at which a solution can become saturated can
change significantly with different environmental factors, such as temperature, pressure, and contamination. For
some solute-solvent combinations a supersaturated solution can be prepared by raising the solubility (for example by
increasing the temperature) to dissolve more solute, and then lowering it (for example by cooling).
Usually, the greater the temperature of the solvent, the more of a given solid solute it can dissolve. However, most
gases and some compounds exhibit solubilities that decrease with increased temperature. Such behavior is a result of
an exothermic enthalpy of solution. Some surfactants exhibit this behaviour. The solubility of liquids in liquids is
generally less temperature-sensitive than that of solids or gases.
Properties
The physical properties of compounds such as melting point and boiling point change when other compounds are
added. Together they are called colligative properties. There are several ways to quantify the amount of one
compound dissolved in the other compounds collectively called concentration. Examples include molarity, mole
fraction, and parts per million (PPM).
The properties of ideal solutions can be calculated by the linear combination of the properties of its components. If
both solute and solvent exist in equal quantities (such as in a 50% ethanol, 50% water solution), the concepts of
"solute" and "solvent" become less relevant, but the substance that is more often used as a solvent is normally
designated as the solvent (in this example, water).
287
Solution
288
Liquid solutions
In principle, all types of liquids can behave as solvents: liquid noble gases, molten metals, molten salts, molten
covalent networks, and molecular liquids. In the practice of chemistry and biochemistry, most solvents are molecular
liquids. They can be classified into polar and non-polar, according to whether their molecules possess a permanent
electric dipole moment. Another distinction is whether their molecules are able to form hydrogen bonds (protic and
aprotic solvents). Water, the most commonly used solvent, is both polar and sustains hydrogen bonds.
Salts dissolve in polar solvents, forming positive and negative ions that are
attracted to the negative and positive ends of the solvent molecule,
respectively. If the solvent is water, hydration occurs when the charged solute
ions become surrounded by water molecules. A standard example is aqueous
saltwater. Such solutions are called electrolytes.
For non-ionic solutes, the general rule is: like dissolves like.
Polar solutes dissolve in polar solvents, forming polar bonds or hydrogen
bonds. As an example, all alcoholic beverages are aqueous solutions of
ethanol. On the other hand, non-polar solutes dissolve better in non-polar
solvents. Examples are hydrocarbons such as oil and grease that easily mix
with each other, while being incompatible with water.
An example for the immiscibility of oil and water is a leak of petroleum from
a damaged tanker, that does not dissolve in the ocean water but rather floats on the surface.
Solution
References
IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version:
(2006) "solution [1]".
[1] http:/ / goldbook. iupac. org/ S05746. html
Acid
An acid (from the Latin acidus/acre meaning sour[1] ) is a substance
which reacts with a base. Commonly, acids can be identified as tasting
sour, reacting with metals such as calcium, and bases like sodium
carbonate. Aqueous acids have a pH of less than 7, where an acid of
lower pH is typically stronger, and turn blue litmus paper red.
Chemicals or substances having the property of an acid are said to be
acidic.
Common examples of acids include acetic acid (in vinegar), sulfuric
acid (used in car batteries), and tartaric acid (used in baking). As these
Zinc, a typical metal, reacting with hydrochloric
three examples show, acids can be solutions, liquids, or solids. Gases
acid, a typical acid
such as hydrogen chloride can be acids as well. Strong acids and some
concentrated weak acids are corrosive, but there are exceptions such as carboranes and boric acid.
There are three common definitions for acids: the Arrhenius definition, the Brnsted-Lowry definition, and the
Lewis definition. The Arrhenius definition states that acids are substances which increase the concentration of
hydronium ions (H3O+) in solution. The Brnsted-Lowry definition is an expansion: an acid is a substance which can
act as a proton donor. Most acids encountered in everyday life are aqueous solutions, or can be dissolved in water,
and these two definitions are most relevant. The reason why pHs of acids are less than 7 is that the concentration of
hydronium ions is greater than 107 moles per liter. Since pH is defined as the negative logarithm of the
concentration of hydronium ions, acids thus have pHs of less than 7. By the Brnsted-Lowry definition, any
compound which can easily be deprotonated can be considered an acid. Examples include alcohols and amines
which contain O-H or N-H fragments.
In chemistry, the Lewis definition of acidity is frequently encountered. Lewis acids are electron-pair acceptors.
Examples of Lewis acids include all metal cations, and electron-deficient molecules such as boron trifluoride and
aluminium trichloride. Hydronium ions are acids according to all three definitions. Interestingly, although alcohols
and amines can be Brnsted-Lowry acids as mentioned above, they can also function as Lewis bases due to the lone
pairs of electrons on their oxygen and nitrogen atoms.
289
Acid
290
Arrhenius acids
The Swedish chemist Svante Arrhenius attributed the properties of acidity to hydrogen in 1884. An Arrhenius acid
is a substance that increases the concentration of the hydronium ion, H3O+, when dissolved in water. This definition
stems from the equilibrium dissociation of water into hydronium and hydroxide (OH) ions:[2]
H2O(l) + H2O(l)
H3O+(aq) + OH(aq)
In pure water the majority of molecules exist as H2O, but a small number of molecules are constantly dissociating
and re-associating. Pure water is neutral with respect to acidity or basicity because the concentration of hydroxide
ions is always equal to the concentration of hydronium ions. An Arrhenius base is a molecule which increases the
concentration of the hydroxide ion when dissolved in water. Note that chemists often write H+(aq) and refer to the
hydrogen ion when describing acid-base reactions but the free hydrogen nucleus, a proton, does not exist alone in
water, it exists as the hydronium ion, H3O+ .
Brnsted-Lowry acids
While the Arrhenius concept is useful for describing many reactions, it is also quite limited in its scope. In 1923
chemists Johannes Nicolaus Brnsted and Thomas Martin Lowry independently recognized that acid-base reactions
involve the transfer of a proton. A Brnsted-Lowry acid (or simply Brnsted acid) is a species that donates a proton
to a Brnsted-Lowry base.[2] Brnsted-Lowry acid-base theory has several advantages over Arrhenius theory.
Consider the following reactions of acetic acid (CH3COOH), the organic acid that gives vinegar its characteristic
taste:
Both theories easily describe the first reaction: CH3COOH acts as an Arrhenius acid because it acts as a source of
H3O+ when dissolved in water, and it acts as a Brnsted acid by donating a proton to water. In the second example
CH3COOH undergoes the same transformation, in this case donating a proton to ammonia (NH3), but cannot be
described using the Arrhenius definition of an acid because the reaction does not produce hydronium.
Brnsted-Lowry theory can also be used to describe molecular compounds, whereas Arrhenius acids must be ionic
compounds. Hydrogen chloride (HCl) and ammonia combine under several different conditions to form ammonium
chloride, NH4Cl. In aqueous solution HCl behaves as hydrochloric acid and exists as hydronium and chloride ions.
The following reactions illustrate the limitations of Arrhenius's definition:
1. H3O+(aq) + Cl(aq) + NH3 Cl(aq) + NH4+(aq)
2. HCl(benzene) + NH3(benzene) NH4Cl(s)
3. HCl(g) + NH3(g) NH4Cl(s)
Acid
291
As with the acetic acid reactions, both definitions work for the first example, where water is the solvent and
hydronium ion is formed. The next two reactions do not involve the formation of ions but are still proton transfer
reactions. In the second reaction hydrogen chloride and ammonia (dissolved in benzene) react to form solid
ammonium chloride in a benzene solvent and in the third gaseous HCl and NH3 combine to form the solid.
Lewis acids
A third concept was proposed in 1923 by Gilbert N. Lewis which includes reactions with acid-base characteristics
that do not involve a proton transfer. A Lewis acid is a species that accepts a pair of electrons from another species;
in other words, it is an electron pair acceptor.[2] Brnsted acid-base reactions are proton transfer reactions while
Lewis acid-base reactions are electron pair transfers. All Brnsted acids are also Lewis acids, but not all Lewis acids
are Brnsted acids. Contrast the following reactions which could be described in terms of acid-base chemistry.
In the first reaction a fluoride ion, F, gives up an electron pair to boron trifluoride to form the product
tetrafluoroborate. Fluoride "loses" a pair of valence electrons because the electrons shared in the BF bond are
located in the region of space between the two atomic nuclei and are therefore more distant from the fluoride nucleus
than they are in the lone fluoride ion. BF3 is a Lewis acid because it accepts the electron pair from fluoride. This
reaction cannot be described in terms of Brnsted theory because there is no proton transfer. The second reaction can
be described using either theory. A proton is transferred from an unspecified Brnsted acid to ammonia, a Brnsted
base; alternatively, ammonia acts as a Lewis base and transfers a lone pair of electrons to form a bond with a
hydrogen ion. The species that gains the electron pair is the Lewis acid; for example, the oxygen atom in H3O+ gains
a pair of electrons when one of the HO bonds is broken and the electrons shared in the bond become localized on
oxygen. Depending on the context, a Lewis acid may also be described as an oxidizer or an electrophile.
The Brnsted-Lowry definition is the most widely used definition; unless otherwise specified acid-base reactions are
assumed to involve the transfer of a proton (H+) from an acid to a base.
Acid
292
The stronger of two acids will have a higher Ka than the weaker acid; the ratio of hydrogen ions to acid will be higher
for the stronger acid as the stronger acid has a greater tendency to lose its proton. Because the range of possible
values for Ka spans many orders of magnitude, a more manageable constant, pKa is more frequently used, where pKa
= -log10 Ka. Stronger acids have a smaller pKa than weaker acids. Experimentally determined pKa at 25C in aqueous
solution are often quoted in textbooks and reference material.
Nomenclature
In the classical naming system, acids are named according to their anions. That ionic suffix is dropped and replaced
with a new suffix (and sometimes prefix), according to the table below. For example, HCl has chloride as its anion,
so the -ide suffix makes it take the form hydrochloric acid. In the IUPAC naming system, "aqueous" is simply added
to the name of the ionic compound. Thus, for hydrogen chloride, the IUPAC name would be aqueous hydrogen
chloride. The prefix "hydro-" is added only if the acid is made up of just hydrogen and one other element.
Classical naming system:
Anion prefix
Anion suffix
Acid prefix
Acid suffix
per
ate
per
ic acid
ate
ic acid
ite
ous acid
hypo
Example
ite
hypo
ous acid
ide
hydro
ic acid
Acid strength
The strength of an acid refers to its ability or tendency to lose a proton. A strong acid is one that completely
dissociates in water; in other words, one mole of a strong acid HA dissolves in water yielding one mole of H+ and
one mole of the conjugate base, A, and none of the protonated acid HA. In contrast a weak acid only partially
dissociates and at equilibrium both the acid and the conjugate base are in solution. Examples of strong acids are
hydrochloric acid (HCl), hydroiodic acid (HI), hydrobromic acid (HBr), perchloric acid (HClO4), nitric acid (HNO3)
and sulfuric acid (H2SO4). In water each of these essentially ionizes 100%. The stronger an acid is, the more easily it
loses a proton, H+. Two key factors that contribute to the ease of deprotonation are the polarity of the HA bond
and the size of atom A, which determines the strength of the HA bond. Acid strengths are also often discussed in
terms of the stability of the conjugate base.
Stronger acids have a larger Ka and a more negative pKa than weaker acids.
Sulfonic acids, which are organic oxyacids, are a class of strong acids. A common example is toluenesulfonic acid
(tosylic acid). Unlike sulfuric acid itself, sulfonic acids can be solids. In fact, polystyrene functionalized into
polystyrene sulfonate is a solid strongly acidic plastic that is filterable.
Superacids are acids stronger than 100% sulfuric acid. Examples of superacids are fluoroantimonic acid, magic acid
and perchloric acid. Superacids can permanently protonate water to give ionic, crystalline hydronium "salts". They
can also quantitatively stabilize carbocations.
Acid
293
Name
[3]
pKa
HF
H2O
water
15.7
NH3
ammonia
38
CH4
methane
48
The electronegative element need not be directly bonded to the acidic hydrogen to increase its acidity. An
electronegative atom can pull electron density out of an acidic bond through the inductive effect. The
electron-withdrawing ability diminishes quickly as the electronegative atom moves away from the acidic bond. The
effect is illustrated by the following series of halogenated butanoic acids. Chlorine is more electronegative than
bromine and therefore has a stronger effect. The hydrogen atom bonded to the oxygen is the acidic hydrogen.
Butanoic acid is a carboxylic acid.
Structure
Name
[4]
pKa
4-chlorobutanoic acid
4.5
3-chlorobutanoic acid
4.0
2-bromobutanoic acid
2.93
2-chlorobutanoic acid
2.86
As the chlorine atom moves further away from the acidic OH bond, its effect diminishes. When the chlorine atom
is just one carbon removed from the carboxylic acid group the acidity of the compound increases significantly,
compared to butanoic acid (a.k.a. butyric acid). However, when the chlorine atom is separated by several bonds the
effect is much smaller. Bromine is much more electronegative than either carbon or hydrogen, but not as
Acid
294
electronegative as chlorine, so the pKa of 2-bromobutanoic acid is slightly greater than the pKa of 2-chlorobutanoic
acid.
Carboxylic acids are organic acids that contain an acidic hydroxyl group and a carbonyl (C=O bond). Carboxylic
acids can be reduced to the corresponding alcohol; the replacement of an electronegative oxygen atom with two
electropositive hydrogens yields a product which is essentially non-acidic. The reduction of acetic acid to ethanol
using LiAlH4 (lithium aluminium hydride or LAH) and ether is an example of such a reaction.
The pKa for ethanol is 16, compared to 4.76 for acetic acid.[4] [6]
Acid
295
Chemical characteristics
Monoprotic acids
Monoprotic acids are those acids that are able to donate one proton per molecule during the process of dissociation
(sometimes called ionization) as shown below (symbolized by HA):
HA(aq) + H2O(l)
H3O+(aq) + A(aq) Ka
Common examples of monoprotic acids in mineral acids include hydrochloric acid (HCl) and nitric acid (HNO3). On
the other hand, for organic acids the term mainly indicates the presence of one carboxylic acid group and sometimes
these acids are known as monocarboxylic acid. Examples in organic acids include formic acid (HCOOH), acetic acid
(CH3COOH) and benzoic acid (C6H5COOH).
Polyprotic acids
Polyprotic acids, also known as polybasic acids, are able to donate more than one proton per acid molecule, in
contrast to monoprotic acids that only donate one proton per molecule. Specific types of polyprotic acids have more
specific names, such as diprotic acid (two potential protons to donate) and triprotic acid (three potential protons to
donate).
A diprotic acid (here symbolized by H2A) can undergo one or two dissociations depending on the pH. Each
dissociation has its own dissociation constant, Ka1 and Ka2.
H2A(aq) + H2O(l)
HA(aq) + H2O(l)
The first dissociation constant is typically greater than the second; i.e., Ka1 > Ka2. For example, sulfuric acid (H2SO4)
can donate one proton to form the bisulfate anion (HSO4), for which Ka1 is very large; then it can donate a second
proton to form the sulfate anion (SO42-), wherein the Ka2 is intermediate strength. The large Ka1 for the first
dissociation makes sulfuric a strong acid. In a similar manner, the weak unstable carbonic acid (H2CO3) can lose one
proton to form bicarbonate anion (HCO3) and lose a second to form carbonate anion (CO32-). Both Ka values are
small, but Ka1 > Ka2 .
A triprotic acid (H3A) can undergo one, two, or three dissociations and has three dissociation constants, where Ka1 >
Ka2 > Ka3.
H3A(aq) + H2O(l)
HA2(aq) + H2O(l)
H2A(aq) + H2O(l)
An inorganic example of a triprotic acid is orthophosphoric acid (H3PO4), usually just called phosphoric acid. All
three protons can be successively lost to yield H2PO4, then HPO42-, and finally PO43-, the orthophosphate ion,
usually just called phosphate. An organic example of a triprotic acid is citric acid, which can successively lose three
protons to finally form the citrate ion. Even though the positions of the protons on the original molecule may be
equivalent, the successive Ka values will differ since it is energetically less favorable to lose a proton if the conjugate
base is more negatively charged.
Although the subsequent loss of each hydrogen ion is less favorable, all of the conjugate bases are present in
solution. The fractional concentration, (alpha), for each species can be calculated. For example, a generic diprotic
acid will generate 3 species in solution: H2A, HA-, and A2-. The fractional concentrations can be calculated as below
when given either the pH (which can be converted to the [H+]) or the concentrations of the acid with all its conjugate
bases:
Acid
296
A pattern is observed in the above equations and can be expanded to the general n -protic acid that has been
deprotonated i -times:
where K0 = 1 and the other K-terms are the dissociation constants for the
acid.
Neutralization
Neutralization is the reaction between an acid and a base, producing a
salt and neutralized base; for example, hydrochloric acid and sodium
hydroxide form sodium chloride and water:
HCl(aq) + NaOH(aq) H2O(l) + NaCl(aq)
Neutralization is the basis of titration, where a pH indicator shows
equivalence point when the equivalent number of moles of a base have
been added to an acid. It is often wrongly assumed that neutralization
should result in a solution with pH 7.0, which is only the case with
similar acid and base strengths during a reaction.
Neutralization with a base weaker than the acid results in a weakly
acidic salt. An example is the weakly acidic ammonium chloride,
which is produced from the strong acid hydrogen chloride and the
weak base ammonia. Conversely, neutralizing a weak acid with a
strong base gives a weakly basic salt, e.g. sodium fluoride from
hydrogen fluoride and sodium hydroxide.
Acid
297
Applications of acids
There are numerous uses for acids. Acids are often used to remove rust and other corrosion from metals in a process
known as pickling. They may be used as an electrolyte in a wet cell battery, such as sulfuric acid in a car battery.
Strong acids, sulfuric acid in particular, are widely used in mineral processing. For example, phosphate minerals
react with sulfuric acid to produce phosphoric acid for the production of phosphate fertilizers, and zinc is produced
by dissolving zinc oxide into sulfuric acid, purifying the solution and electrowinning.
In the chemical industry, acids react in neutralization reactions to produce salts. For example, nitric acid reacts with
ammonia to produce ammonium nitrate, a fertilizer. Additionally, carboxylic acids can be esterified with alcohols, to
produce esters.
Acids are used as additives to drinks and foods, as they alter their taste and serve as preservatives. Phosphoric acid,
for example, is a component of cola drinks. Acetic acid is used in day to day life as vinegar. Carbonic acid is an
important part of some cola drinks and soda. Citric acid is used as a preservative in sauces and pickles.
Tartaric acid is an important component of some commonly used foods like unripened mangoes and tamarind.
Natural fruits and vegetables also contain acids. Citric acid is present in oranges, lemon and other citrus fruits.
Oxalic acid is present in tomatoes, spinach, and especially in carambola and rhubarb; rhubarb leaves and unripe
carambolas are toxic because of high concentrations of oxalic acid.
Ascorbic acid (Vitamin C) is an essential vitamin required in our body and is present in such foods as amla, lemon,
citrus fruits, and guava.
Certain acids are used as drugs. Acetylsalicylic acid (Aspirin) is used as a pain killer and for bringing down fevers.
Acids play very important roles in the human body. The hydrochloric acid present in our stomach aids in digestion
by breaking down large and complex food molecules. Amino acids are required for synthesis of proteins required for
growth and repair of our body tissues. Fatty acids are also required for growth and repair of body tissues. Nucleic
acids are important for the manufacturing of DNA, RNA and transmission of characters to offspring through genes.
Carbonic acid is important for maintenance of pH equilibrium in the body.
Acid catalysis
Acids are used as catalysts in industrial and organic chemistry; for example, sulfuric acid is used in very large
quantities in the alkylation process to produce gasoline. Strong acids, such as sulfuric, phosphoric and hydrochloric
acids also effect dehydration and condensation reactions. In biochemistry, many enzymes employ acid catalysis.[7]
Biological occurrence
Many biologically important molecules are acids. Nucleic acids, which
contain acidic phosphate groups, include DNA and RNA. Nucleic acids
contain the genetic code that determines many of an organism's
characteristics, and is passed from parents to offspring. DNA contains
the chemical blueprint for the synthesis of proteins which are made up of
amino acid subunits. Cell membranes contain fatty acid esters such as
phospholipids.
many of the properties of a specific amino acid. In glycine, the simplest amino acid, the R group is a hydrogen atom,
but in all other amino acids it is contains one or more carbon atoms bonded to hydrogens, and may contain other
Acid
298
elements such as sulfur, oxygen or nitrogen. With the exception of glycine, naturally occurring amino acids are
chiral and almost invariably occur in the L-configuration. Peptidoglycan, found in some bacterial cell walls contains
some D-amino acids. At physiological pH, typically around 7, free amino acids exist in a charged form, where the
acidic carboxyl group (-COOH) loses a proton (-COO) and the basic amine group (-NH2) gains a proton (-NH3+).
The entire molecule has a net neutral charge and is a zwitterion, with the exception of amino acids with basic or
acidic side chains. Aspartic acid, for example, possesses one protonated amine and two deprotonated carboxyl
groups, for a net charge of -1 at physiological pH.
Fatty acids and fatty acid derivatives are another group of carboxylic acids that play a significant role in biology.
These contain long hydrocarbon chains and a carboxylic acid group on one end. The cell membrane of nearly all
organisms is primarily made up of a phospholipid bilayer, a micelle of hydrophobic fatty acid esters with polar,
hydrophilic phosphate "head" groups. Membranes contain additional components, some of which can participate in
acid-base reactions.
In humans and many other animals, hydrochloric acid is a part of the gastric acid secreted within the stomach to help
hydrolyze proteins and polysaccharides, as well as converting the inactive pro-enzyme, pepsinogen into the enzyme,
pepsin. Some organisms produce acids for defense; for example, ants produce formic acid.
Acid-base equilibrium plays a critical role in regulating mammalian breathing. Oxygen gas (O2) drives cellular
respiration, the process by which animals release the chemical potential energy stored in food, producing carbon
dioxide (CO2) as a byproduct. Oxygen and carbon dioxide are exchanged in the lungs, and the body responds to
changing energy demands by adjusting the rate of ventilation. For example, during periods of exertion the body
rapidly breaks down stored carbohydrates and fat, releasing CO2 into the blood stream. In aqueous solutions such as
blood CO2 exists in equilibrium with carbonic acid and bicarbonate ion.
CO2 + H2O
H2CO3
H+ + HCO3
It is the decrease in pH that signals the brain to breathe faster and deeper, expelling the excess CO2 and resupplying
the cells with O2.
Cell membranes are generally impermeable to charged or large, polar
molecules because of the lipophilic fatty acyl chains comprising their
interior. Many biologically important molecules, including a number of
pharmaceutical agents, are organic weak acids which can cross the
membrane in their protonated, uncharged form but not in their charged
form (i.e. as the conjugate base). For this reason the activity of many
drugs can be enhanced or inhibited by the use of antacids or acidic
foods. The charged form, however, is often more soluble in blood and
cytosol, both aqueous environments. When the extracellular
environment is more acidic than the neutral pH within the cell, certain
Aspirin (acetylsalicylic acid) is a carboxylic acid.
acids will exist in their neutral form and will be membrane soluble,
allowing them to cross the phospholipid bilayer. Acids that lose a
proton at the intracellular pH will exist in their soluble, charged form and are thus able to diffuse through the cytosol
to their target. Ibuprofen, aspirin and penicillin are examples of drugs that are weak acids.
Acid
299
Common acids
Mineral acids (inorganic acids)
Hydrogen halides and their solutions: hydrochloric acid (HCl), hydrobromic acid (HBr), hydroiodic acid (HI)
Halogen oxoacids: hypochlorous acid (HClO), chlorous acid (HClO2), chloric acid (HClO3), perchloric acid
(HClO4), and corresponding compounds for bromine and iodine
Sulfuric acid (H2SO4)
Fluorosulfuric acid (HSO3F)
Nitric acid (HNO3)
Phosphoric acid (H3PO4)
Fluoroantimonic acid (HSbF6)
Fluoroboric acid (HBF4)
Hexafluorophosphoric acid (HPF6)
Chromic acid (H2CrO4)
Boric acid (H3BO3)
Sulfonic acids
Carboxylic acids
Nucleic acids
Deoxyribonucleic acid (DNA)
Ribonucleic acid (RNA)
References
[1] Merriam-Webster's Online Dictionary: acid (http:/ / www. merriam-webster. com/ dictionary/ acid)
[2] Ebbing, D.D., & Gammon, S. D. (2005). General chemistry (8th ed.). Boston, MA: Houghton Mifflin. ISBN 0-618-51177-6
[3] pKa's of Inorganic and Oxo-Acids (http:/ / www2. lsdiv. harvard. edu/ labs/ evans/ pdf/ evans_pKa_table. pdf)
[4] Section 8: Electrolytes, Electromotive forces and Chemical Equilibrium (http:/ / www. scribd. com/ doc/ 6792576/ 638478)
Acid
300
[5] pKa values for HClOn from Housecroft, C. E.; Sharpe, A. G. (2004). Inorganic Chemistry (2nd ed.). Prentice Hall. ISBN978-0130399137.
[6] pKa Data Compiled by R. Williams (http:/ / research. chem. psu. edu/ brpgroup/ pKa_compilation. pdf)
[7] Voet, Judith G.; Voet, Donald (2004). Biochemistry. New York: J. Wiley & Sons. pp.496500. ISBN9780471193500.
External links
Science Aid: Acids and Bases (http://scienceaid.co.uk/chemistry/physical/acidbases.html) Information for
High School students
Curtipot (http://www2.iq.usp.br/docente/gutz/Curtipot_.html): Acid-Base equilibria diagrams, pH
calculation and titration curves simulation and analysis - freeware
A summary of the Properties of Acids for the beginning chemistry student (http://canadaconnects.ca/chemistry/
10081/)
The UN ECE Convention on Long-Range Transboundary Air Pollution (http://www.unece.org/env/lrtap/)
Chem 106 - Acidity Concepts (http://isites.harvard.edu/fs/docs/icb.topic776365.files/lecture 17.pdf)
Reductionoxidation
Redox
(portmanteau
for
reduction-oxidation) reactions describe all
chemical reactions in which atoms have
their oxidation state changed. This can be
either a simple redox process, such as the
oxidation of carbon to yield carbon dioxide
(CO2) or the reduction of carbon by
hydrogen to yield methane (CH4), or a
complex process such as the oxidation of
glucose (C6H12O6) in the human body
through a series of complex electron transfer processes.
Reductionoxidation
301
defined as an increase in oxidation state, and reduction as a decrease in oxidation state. In practice, the transfer of
electrons will always cause a change in oxidation state, but there are many reactions that are classed as "redox" even
though no electron transfer occurs (such as those involving covalent bonds).
Non-redox reactions, which do not involve changes in formal charge, are known as metathesis reactions.
Oxidizers
Substances that have the ability to oxidize
other substances are said to be oxidative or
oxidizing and are known as oxidizing
agents, oxidants, or oxidizers. Put another
way, the oxidant (oxidizing agent) removes
electrons from another substance; i.e., it
oxidizes other substances, and is thus itself
reduced. And, because it "accepts"
electrons, it is also called an electron
acceptor.
Rusting iron
Reducers
Substances that have the ability to reduce
other substances are said to be reductive or
A bonfire. Combustion consists of redox reactions involving free
reducing and are known as reducing agents,
radicals.
reductants, or reducers. The reductant
(reducing agent) transfers electrons to
another substance; i.e., it reduces others, and is thus itself oxidized. And, because it "donates" electrons, it is also
called an electron donor. Electron donors can also form charge transfer complexes with electron acceptors.
Reductionoxidation
Reductants in chemistry are very diverse. Electropositive elemental metals, such as lithium, sodium, magnesium,
iron, zinc, and aluminium, are good reducing agents. These metals donate or give away electrons readily. Hydride
transfer reagents, such as NaBH4 and LiAlH4, are widely used in organic chemistry,[1] [2] primarily in the reduction
of carbonyl compounds to alcohols. Another method of reduction involves the use of hydrogen gas (H2) with a
palladium, platinum, or nickel catalyst. These catalytic reductions are used primarily in the reduction of
carbon-carbon double or triple bonds.
302
Reductionoxidation
303
H2
F2 + 2 e
H2 + F2
2 H+ + 2 e
2 F
2 H+ + 2 F
Displacement reactions
Redox occurs in single displacement reactions or substitution reactions. The redox component of these types of
reactions is the change of oxidation state (charge) on certain atoms, not the actual exchange of atoms in the
compounds.
For example, in the reaction between iron and copper(II) sulfate solution:
Fe + CuSO4 FeSO4 + Cu
The ionic equation for this reaction is:
Fe + Cu2+ Fe2+ + Cu
As two half-equations, it is seen that the iron is oxidized:
Fe Fe2+ + 2 e
And the copper is reduced:
Cu2+ + 2 e Cu
Other examples
The oxidation of iron(II) to iron(III) by hydrogen peroxide in the presence of an acid:
Fe2+ Fe3+ + e
H2O2 + 2 e 2 OH
Overall equation:
2 Fe2+ + H2O2 + 2 H+ 2 Fe3+ + 2 H2O
The reduction of nitrate to nitrogen in the presence of an acid (denitrification):
2 NO3 + 10 e + 12 H+ N2 + 6 H2O
Oxidation of elemental iron to iron(III) oxide by oxygen (commonly
known as rusting, which is similar to tarnishing):
4 Fe + 3 O2 2 Fe2O3
The combustion of hydrocarbons, such as in an internal combustion
engine, which produces water, carbon dioxide, some partially
oxidized forms such as carbon monoxide, and heat energy.
Complete oxidation of materials containing carbon produces carbon
dioxide.
In organic chemistry, the stepwise oxidation of a hydrocarbon by
oxygen produces water and, successively, an alcohol, an aldehyde
or a ketone, a carboxylic acid, and then a peroxide.
Reductionoxidation
304
Reductionoxidation
305
Redox cycling
A wide variety of aromatic compounds are enzymatically reduced to form free radicals that contain one more
electron than their parent compounds. In general, the electron donor is any of a wide variety of flavoenzymes and
their coenzymes. Once formed, these anion free radicals reduce molecular oxygen to superoxide, and regenerate the
unchanged parent compound. The net reaction is the oxidation of the flavoenzyme's coenzymes and the reduction of
molecular oxygen to form superoxide. This catalytic behavior has been described as futile cycle or redox cycling.
Examples of redox cycling-inducing molecules are the herbicide paraquat and other viologens and quinones such as
menadione.[3]
Acidic media
In acidic media, H+ ions and water are added to half reactions to balance the overall reaction.
For example, when manganese(II) reacts with sodium bismuthate:
Unbalanced reaction: Mn2+(aq) + NaBiO (s) Bi3+(aq) + MnO (aq)
3
4
Oxidation:
Reduction:
The reaction is balanced by scaling the two half-cell reactions to involve the same number of electrons (multiplying
the oxidation reaction by the number of electrons in the reduction step and vice versa):
8 H2O(l) + 2 Mn2+(aq) 2 MnO(aq) + 16 H+(aq) + 10 e
10 e + 30 H+ + 5 BiO(s) 5 Bi3+(aq) + 15 H2O(l)
Adding these two reactions eliminates the electrons terms and yields the balanced reaction:
14 H+(aq) + 2 Mn2+(aq) + 5 NaBiO3(s) 7 H2O(l) + 2 MnO(aq) + 5 Bi3+(aq) + 5 Na+(aq)
Reductionoxidation
306
Basic media
In basic media, OH ions and water are added to half reactions to balance the overall reaction.
For example, in the reaction between potassium permanganate and sodium sulfite:
Unbalanced reaction: KMnO4 + Na2SO3 + H2O MnO2 + Na2SO4 + KOH
Reduction:
Oxidation:
Memory aids
The key terms involved in redox are often confusing to students.[4] [5] For example, an element that is oxidized loses
electrons; however, that element is referred to as the reducing agent. Likewise, an element that is reduced gains
electrons and is referred to as the oxidizing agent.[6] Acronyms or mnemonics are commonly used[7] to help
remember what is happening:
"LEO the lion says GER" Loss of Electrons is Oxidation, Gain of Electrons is Reduction.[4] [5] [7] [6]
"LEORA says GEROA" Loss of Electrons is Oxidation (Reducing Agent) and Gain of Electrons is Reduced
(Oxidizing Agent).[6]
"OIL RIG"Oxidation Is Loss of electrons, Reduction Is Gain of electrons.[4] [5] [7] [6]
References
[1]
[2]
[3]
[4]
Hudlick, Milo (1996). Reductions in Organic Chemistry. Washington, D.C.: American Chemical Society. pp.429. ISBN0-8412-3344-6.
Hudlick, Milo (1990). Oxidations in Organic Chemistry. Washington, D.C.: American Chemical Society. pp.456. ISBN0-8412-1780-7.
"gutier.doc" (http:/ / www. bioscience. org/ 2000/ v5/ d/ gutier/ gutier. pdf). . Retrieved 2008-06-30.PDF(2.76MiB)
Robertson, William (2010). More Chemistry Basics (http:/ / books. google. com/ books?id=hIzuarlXtH4C& pg=PA82& dq=confusing).
National Science Teachers Association. p.82. ISBN978-1-936137-74-9. .
[5] Phillips, John; Strozak, Victor; Wistrom, Cheryl (2000). Chemistry: Concepts and Applications. Glencoe McGraw-Hill. p.558.
ISBN978-0028282107. "Students often are confused when associating reduction with the gain of electrons."
[6] Rodgers, Glen (2012). Descriptive Inorganic, Coordination, and Solid-State Chemistry (http:/ / books. google. com/
books?id=g_ybia0hGw8C& pg=PA330). Brooks/Cole, Cengage Learning. p.330. ISBN978-0-8400-6846-0. .
[7] Zumdahl, Steven; Zumdahl, Susan (2009). Chemistry (http:/ / books. google. com/ books?id=IdhYqXy37KIC& pg=PA160). Houghton
Mifflin. p.160. ISBN978-0-547-05405-6. .
Schring, J., Schulz, H. D., Fischer, W. R., Bttcher, J., Duijnisveld, W. H. (editors)(1999). Redox:
Fundamentals, Processes and Applications, Springer-Verlag, Heidelberg, 246 pp.ISBN 978-3-540-66528-1 (pdf
3,6 MB) (http://hdl.handle.net/10013/epic.31694.d001)
Reductionoxidation
External links
Chemical Equation Balancer (http://www.berkeleychurchill.com/software/chembal.php) - An open source
chemical equation balancer that handles redox reactions.
Video - Synthesis of Copper(II) Acetate (http://www.youtube.com/watch?v=rF1ls-v7puQ) 20 Feb. 2009
Redox reactions calculator (http://www.shodor.org/UNChem/advanced/redox/redoxcalc.html)
Redox reactions at Chemguide (http://www.chemguide.co.uk/inorganic/redox/definitions.html#top)
Online redox reaction equation balancer, balances equations of any half-cell and full reactions (http://www.
webqc.org/balance.php)
307
308
Miscellaneous
Etymology
In the history of science, the etymology of the word chemistry is a debatable issue. It is agreed that the word
derives from the word alchemy, which is a European one, derived from the Arabic al-km (). The Arabic term
is derived from the Greek or .[1] [2] However, the ultimate origin of the root word, chem, is uncertain.[3]
According to the Oxford English Dictionary, the majority theory is that al-km is derived from , which is
derived from the ancient Egyptian name of Egypt (khem, khame, or khmi, meaning "black earth", contrasting with
the surrounding desert.) Therefore, alchemy is the "Egyptian art".[1] However, it is also possible that al-km was
derived from , meaning "cast together".[4]
Traditionally, the science of alchemy was once considered to have sprung from great Egyptian figure named by the
Greeks "Hermes Trismegistus" (the "thrice-great" Hermes, celebrated as priest, king, and scholar), who is thought to
have been the founder of the art.[5] Reputed to have lived about 1900 B.C., he was highly celebrated for his wisdom
and skill in the operations of nature. In 1614 Isaac Casaubon demonstrated that the works attributed to Hermes the
so-called "Hermetic corpus" were actually written pseudonymously during the first three centuries of the Common
Era.
Overview
The first documents written in ancient Greek date from around 800 B.C.[6] more than 1,000 years after literary
Egyptian; so Greek alchemists may have adopted Egyptian terminology.[7] Other possible sources include the Old
Persian word "Kimiya" meaning gold. The alchemical theories associated with Hermes Trismegistus, is the
syncretism of the Greek god Hermes and the Egyptian Thoth.[8] Moreover, it is known that "[t]he four chemical gods
of the Egyptians, the female-male original principle of Osiris (male Sun) and the corresponding Isis (Wife-sister,
female Moon), as well as Mercury and Vulcan, became eight gods and finally twelve gods, who were later taken
over by the Greeks."[9] This origin theory, in chemistry, was generally known as the "pyramid of composition" and
was utilized in the writing of Michael Maier, who in turn influenced Isaac Newton in his alchemical writings in the
1680s. Hence, the ancient "Egypt" word kme (3000 B. C.), which stands for earth, is a possible root word of
chemistry; this later became "khmia", or transmutation, by 300 AD, and then al-khemia in the Arabic world, then
alchemia in the Dark Ages, then chymistry in 1661 with Boyles publication, and now chemistry.
In Alexandria alchemy began to flourish in the Hellenistic period; simultaneously, a school of alchemy was
developing in China. The writings of some of the early Greek philosophers might be considered to contain the first
chemical theories; and the theory advanced in the 5th century B. C. by Empedocles that all things are composed
of air, earth, fire, and water was influential in alchemy.[10]
J. R. Partington in his four-volume work History of Chemistry (1969) [11] says that the earliest applications of
chemical processes were concerned with the extraction and working of metals and the manufacture of pottery, which
were forms of crafts practiced many centuries before the Bronze Age cultures of Egypt and Mesopotamia. Thus,
according to Partington, alchemy preceded Egypt and Mesopotamia.[12]
There are two main views on the derivation of the word, which agree in holding that it has an Arabic descent, the
prefix al being the Arabic article. But according to one, the second part of the word comes from the Greek ,
pouring, infusion, used in connexion with the study of the juices of plants, and thence extended to chemical
manipulations in general; this derivation accounts for the old-fashioned spellings "chymist" and "chymistry". The
other view traces it to khem or khame, hieroglyph khmi, which denotes black earth as opposed to barren sand, and
Etymology
309
occurs in Plutarch as ; on this derivation alchemy is explained as meaning the "Egyptian art". The first
occurrence of the word is said to be in a treatise of Julius Firmicus, an astrological writer of the 4th century, but the
prefix al there must be the addition of a later copyist. In English, Piers Plowman (1362) contains the phrase
"experimentis of alconomye", with variants "alkenemye" and " alknamye". The prefix al began to be dropped about
the middle of the 16th century (further details of which are given below).[13]
Egyptian origin
According to the Egyptologist Wallis Budge, the Arabic word al-kmiya actually means "the Egyptian [science]",
borrowing from the Coptic word for "Egypt", kme (or its equivalent in the Mediaeval Bohairic dialect of Coptic,
khme). This Coptic word derives from Demotic km, itself from ancient Egyptian kmt. The ancient Egyptian word
referred to both the country and the colour "black" (Egypt was the "Black Land", by contrast with the "Red Land",
the surrounding desert); so this etymology could also explain the nickname "Egyptian black arts". However,
according to Mahn, this theory may be an example of folk etymology.[14] Assuming an Egyptian origin, chemistry is
defined as follows:
Chemistry, from the ancient Egyptian word "khmia" meaning transmutation of earth, is the science of matter
at the atomic to molecular scale, dealing primarily with collections of atoms, such as molecules, crystals, and
metals.
Thus, according to Budge and others, chemistry derives from an Egyptian word khemein or khmia, "preparation of
black powder", ultimately derived from the name khem, Egypt. A decree of Diocletian, written about 300 AD in
Greek, speaks against "the ancient writings of the Egyptians, which treat of the khmia transmutation of gold and
silver".[15]
Greek origin
Arabic al-kmiya or al-khmiya ( or ), according to some, is thought to derive from the late Greek word
khymeia () meaning "the art of alloying metals, alchemy"; in the manuscripts, this word is also written
khmeia () or kheimeia (),[16] which is the probable basis of the Arabic form. According to Mann, the
Greek word khumeia originally meant "pouring together", "casting together", "weld", "alloy", etc. (cf. Gk.
kheein () "to pour"; khuma(), "that which is poured out, an ingot").[14] Assuming a Greek origin, chemistry
is defined as follows:
Chemistry, from the Greek word (khmeia) meaning "cast together" or "pour together", is the science
of matter at the atomic to molecular scale, dealing primarily with collections of atoms, such as molecules,
crystals, and metals.
Etymology
early translations.
References
[1] "alchemy", entry in The Oxford English Dictionary, J. A. Simpson and E. S. C. Weiner, vol. 1, 2nd ed., 1989, ISBN 0-19-861213-3.
[2] p. 854, "Arabic alchemy", Georges C. Anawati, pp. 853-885 in Encyclopedia of the history of Arabic science, eds. Roshdi Rashed and Rgis
Morelon, London: Routledge, 1996, vol. 3, ISBN 0415124123.
[3] Encyclopedia Britannica, 2002 Edition, CD-ROM
[4] Weekley, Ernest (1967). Etymological Dictionary of Modern English. New York: Dover Publications. ISBN 0486218732
[5] History of Alchemy from Ancient Egypt to Modern Times (http:/ / www. alchemylab. com/ history_of_alchemy. htm) the
AlchemyLab.com
[6] Not including the Linear B tablets from 1300-1100BCE, which are more inventory lists than anything else
[7] Cunliffe, Barry (2001). Atlas of World History. Barnes & Noble. ISBN0760727104.
[8] (Budge The Gods of the Egyptians Vol. 1 p. 415)
[9] Cohen, Bernard, I.; Smith, George, E. (2002). The Cambridge Companion to Newton. Cambridge University Press. ISBN0521656966.
[10] the Alchemists Corner (http:/ / groups. msn. com/ TheAlchemistsCorner/ alchemy. msnw) (this ref is dodgy and doesn't even work for me).
[11] Brock, William, .H. (1992). The Chemical Tree A History of Chemistry. New York: W.W. Norton & Company. ISBN00393320685.
[12] Partington, James, R. (1937). A Short History of Chemistry. New York: Dover Publications, Inc.,. ISBN0486659771.
[13] Encyclopedia Britannica (http:/ / www. 1911encyclopedia. org/ Alchemy) 1911 Edition.
[14] Harper, Douglas. "alchemy" (http:/ / www. etymonline. com/ index. php?term=alchemy). Online Etymology Dictionary. .
[15] Oxford English Dictionary Online, s.v. alchemy
[16] Cf. Liddell-Scott-Jones s.v. .
External links
History of Alchemy (http://www.alchemywebsite.com/timelin2.html) Timeline
Chemical industry
The chemical industry comprises the companies that produce
industrial chemicals. Central to the modern world economy, it converts
raw materials (oil, natural gas, air, water, metals, and minerals) into
more than 70,000 different products.
Products
Polymers and plastics, especially polyethylene, polypropylene,
polyvinyl chloride, polyethylene terephthalate, polystyrene and
Oil refinery in Louisiana - an example of
chemical industry
polycarbonate comprise about 80% of the industrys output worldwide.
Chemicals are used to make a wide variety of consumer goods, as well
as thousands inputs to agriculture, manufacturing, construction, and service industries. The chemical industry itself
consumes 26 percent of its own output. Major industrial customers include rubber and plastic products, textiles,
apparel, petroleum refining, pulp and paper, and primary metals. Chemicals is nearly a $3 trillion global enterprise,
and the EU and U.S. chemical companies are the world's largest producers.
310
Chemical industry
311
Basic chemicals
Basic chemicals, or "commodity chemicals" are a broad
chemical
category
including
polymers,
bulk
petrochemicals and intermediates, other derivatives and
basic industrials, inorganic chemicals, and fertilizers.
Typical growth rates for basic chemicals are about 0.5 to
0.7 times GDP. Product prices are generally less than fifty
cents per pound.
Polymers, the largest revenue segment at about 33
percent of the basic chemicals dollar value, includes all
categories of plastics and man-made fibers. The major
markets for plastics are packaging, followed by home
construction, containers, appliances, pipe, transportation,
toys, and games.
The largest-volume polymer product, polyethylene
(PE), is used mainly in packaging films and other
markets such as milk bottles, containers, and pipe.
Polyvinyl chloride (PVC), another large-volume product, is principally used to make pipe for construction
markets as well as siding and, to a much smaller extent, transportation and packaging materials.
Polypropylene (PP), similar in volume to PVC, is used in markets ranging from packaging, appliances, and
containers to clothing and carpeting.
Polystyrene (PS), another large-volume plastic, is used principally for appliances and packaging as well as toys
and recreation.
The leading man-made fibers include polyester, nylon, polypropylene, and acrylics, with applications including
apparel, home furnishings, and other industrial and consumer use.
The principal raw materials for polymers are bulk petrochemicals.
Chemicals in the bulk petrochemicals and intermediates are primarily made from liquefied petroleum gas (LPG),
natural gas, and crude oil. Their sales volume is close to 30 percent of overall basic chemicals. Typical large-volume
products include ethylene, propylene, benzene, toluene, xylenes, methanol, vinyl chloride monomer (VCM), styrene,
butadiene, and ethylene oxide. These chemicals are the starting points for most polymers and other organic
chemicals as well as much of the specialty chemicals category.
Other derivatives and basic industrials include synthetic rubber, surfactants, dyes and pigments, turpentine, resins,
carbon black, explosives, and rubber products and contribute about 20 percent of the basic chemicals' external sales.
Inorganic chemicals (about 12 percent of the revenue output) make up the oldest of the chemical categories.
Products include salt, chlorine, caustic soda, soda ash, acids (such as nitric acid, phosphoric acid, and sulfuric acid),
titanium dioxide, and hydrogen peroxide.
Fertilizers are the smallest category (about 6 percent) and include phosphates, ammonia, and potash chemicals.
Chemical industry
Life sciences
Life sciences (about 30 percent of the dollar output of the chemistry business) include differentiated chemical and
biological substances, pharmaceuticals, diagnostics, animal health products, vitamins, and pesticides. While much
smaller in volume than other chemical sectors, their products tend to have very high pricesover ten dollars per
poundgrowth rates of 1.5 to 6 times GDP, and research and development spending at 15 to 25 percent of sales.
Life science products are usually produced with very high specifications and are closely scrutinized by government
agencies such as the Food and Drug Administration. Pesticides, also called "crop protection chemicals", are about 10
percent of this category and include herbicides, insecticides, and fungicides.
Specialty chemicals
Specialty chemicals are a category of relatively high valued, rapidly growing chemicals with diverse end product
markets. Typical growth rates are one to three times GDP with prices over a dollar per pound. They are generally
characterized by their innovative aspects. Products are sold for what they can do rather than for what chemicals they
contain. Products include electronic chemicals, industrial gases, adhesives and sealants as well as coatings, industrial
and institutional cleaning chemicals, and catalysts. Coatings make up about 15 percent of specialty chemicals sales,
with other products ranging from 10 to 13 percent. Specialty Chemicals are sometimes referred to as "fine
chemicals"
Consumer products
Consumer products include direct product sale of chemicals such as soaps, detergents, and cosmetics. Typical
growth rates are 0.8 to 1.0 times GDP.
Every year, the American Chemistry Council tabulates the U.S. production volume of the top 100 basic chemicals. In
2000, the aggregate production volume of the top 100 chemicals totalled 502 million tons, up from 397 million tons
in 1990. Inorganic chemicals tend to be the largest volume, though much smaller in dollar revenue terms due to their
low prices. The top 11 of the 100 chemicals in 2000 were sulfuric acid (44 million tons), nitrogen (34), ethylene
(28), oxygen (27), lime (22), ammonia (17), propylene (16), polyethylene (15), chlorine (13), phosphoric acid (13)
and diammonium phosphates (12).
Companies
The largest corporate producers worldwide, each with plants in numerous countries, include BASF, Bayer, Braskem,
Celanese/Ticona, Degussa, Dow, DuPont, Eastman Chemical Company, ExxonMobil, INEOS, Mitsubishi, PPG
Industries, SABIC and Shell, along with thousands of smaller firms.
In the U.S. there are 170 major chemical companies. They operate internationally with more than 2,800 facilities
outside the U.S. and 1,700 foreign subsidiaries or affiliates operating. The U.S. chemical output is $750 billion a
year. The U.S. industry records large trade surpluses and employs more than a million people in the United States
alone. The chemical industry is also the second largest consumer of energy in manufacturing and spends over $5
billion annually on pollution abatement.
In Europe, especially Germany, the chemical, plastics and rubber sectors are among the largest industrial sectors.
Together they generate about 3.2 million jobs in more than 60,000 companies. Since 2000 the chemical sector alone
has represented 2/3 of the entire manufacturing trade surplus of the EU. The chemical sector accounts for 12% of the
EU manufacturing industry's added value.
The chemical industry has shown rapid growth for more than fifty years. The fastest-growing areas have involved
the manufacture of synthetic organic polymers used as plastics, fibres and elastomers. Historically and presently the
chemical industry has been concentrated in three areas of the world, Western Europe, North America and Japan (the
Triad). The European Community remains the largest producer area followed by the USA and Japan.
312
Chemical industry
313
The traditional dominance of chemical production by the Triad countries is being challenged by changes in feedstock
availability and price, labour cost, energy cost, differential rates of economic growth and environmental pressures.
Instrumental in the changing structure of the global chemical industry has been the growth in China, India, Korea,
the Middle East, South East Asia, Nigeria, and Brazil.
Technology
As accepted by chemical engineers, the chemical industry involves the
use of chemical processes such as chemical reactions and refining
methods to produce a wide variety of solid, liquid, and gaseous
materials. Most of these products are used in manufacture of other
items, although a smaller number are used directly by consumers.
Solvents, pesticides, lye, washing soda, and portland cement are a few
examples of product used by consumers.
The industry includes manufacturers of inorganic- and
organic-industrial chemicals, ceramic products, petrochemicals,
agrochemicals, polymers and rubber (elastomers), oleochemicals (oils,
fats, and waxes), explosives, fragrances and flavors. Examples of these
products are shown in the Table below.
Product Type
Examples
inorganic industrial
organic industrial
ceramic products
petrochemicals
agrochemicals
polymers
elastomers
oleochemicals
explosives
Chemical industry
History
Chandler (2005) argues the relative success or failure of American and European chemical companies is explained
with reference to three themes: "barriers to entry," "strategic boundaries," and "limits to growth." He says successful
chemical firms followed definite "paths of learning" whereby first movers and close followers created entry barriers
to would-be rivals by building "integrated learning bases" (or organizational capabilities) which enabled them to
develop, produce, distribute, and sell in local and then worldwide markets. Also they followed a "virtuous strategy"
of reinvestment of retained earnings and growth through diversification, particularly to utilize "dynamic" scale and
scope economies relating to new learning in launching "next generation" products.
314
Chemical industry
315
COMPANY, HEADQUARTERS
BASF SE, Ludwigshafen, Germany
$65.3
$53.5
INEOS, Lyndhurst, UK
$43.6
$42.8
$31.9
$28.5
$26.4
$24.2
$22.2
10
$16.3
11
$15.2
12
$15.0
13
$14.3
14
$13.8
15
$13.1
16
$12.5
17
$12.1
18
$11.2
19
$11.1
20
1998
1999
2000
2001
2002
2003
2004
2005
2006
2008
2009
416.7
420.3
449.2
438.4
462.5
487.7
540.9
610.9
657.7
664.1
689.3
Canada
21.1
21.8
25.0
24.8
25.8
30.5
36.2
40.2
43.7
45.4
47.4
Mexico
19.1
21.0
23.8
24.4
24.3
23.5
25.6
29.2
32.0
33.4
37.8
North America
456.9
463.1
498.0
487.6
512.6
541.7
602.7
680.3
733.4
742.8
774.6
Brazil
46.5
40.0
45.7
41.5
39.6
47.4
60.2
71.1
82.8
96.4
126.7
Other
59.2
58.1
60.8
63.4
58.6
62.9
69.9
77.2
84.6
89.5
102.1
Latin America
105.7
98.1
106.5
104.9
98.2
110.3
130.0
148.3
167.4
185.9
228.8
France
79.1
78.5
76.5
76.8
80.5
99.6
111.1
117.5
121.3
138.4
158.9
Germany
124.9
123.2
118.9
116.1
120.1
148.1
168.6
178.6
192.5
229.5
263.2
Italy
63.9
64.6
59.5
58.6
64.5
75.8
86.6
89.8
95.3
105.9
122.9
United Kingdom
70.3
70.1
66.8
66.4
69.9
77.3
91.3
95.2
107.8
118.2
123.4
Belgium
27.1
27.0
27.5
27.1
28.7
36.1
41.8
43.5
46.9
51.6
62.6
Ireland
16.9
20.1
22.6
22.9
29.1
32.3
33.9
34.9
37.5
46.0
54.8
Netherlands
29.7
29.4
31.3
30.6
32.2
40.1
49.0
52.7
59.2
67.9
81.7
Chemical industry
316
Spain
31.0
30.8
30.8
31.9
33.4
42.0
48.9
52.7
56.7
63.7
74.8
Sweden
11.1
11.4
11.2
11.0
12.5
15.9
18.2
19.3
21.2
21.2
22.6
Switzerland
22.1
22.2
19.4
21.1
25.5
30.3
33.8
35.4
37.8
42.7
53.1
Other
27.1
26.8
25.9
26.4
27.9
33.5
38.6
42.9
46.2
50.3
58.9
Western Europe
503.1
504.0
490.4
488.8
524.4
630.9
721.9
762.7
822.4
935.4
1,076.8
Russia
23.8
24.6
27.4
29.1
30.3
33.4
37.5
40.9
53.1
63.0
77.6
Other
22.3
20.3
21.9
23.4
25.3
31.4
39.6
46.2
55.0
68.4
87.5
Central/Eastern Europe
46.1
44.9
49.3
52.5
55.6
64.8
77.1
87.1
108.0
131.3
165.1
52.7
53.2
59.2
57.4
60.4
73.0
86.4
99.3
109.6
124.2
160.4
Japan
193.8
220.4
239.7
208.3
197.2
218.8
243.6
251.3
248.5
245.4
298.0
215.2
241.9
276.1
271.5
300.5
369.1
463.9
567.5
668.8
795.5
993.2
China
80.9
87.8
103.6
111.0
126.5
159.9
205.0
269.0
331.4
406.4
549.4
India
30.7
35.3
35.3
32.5
33.5
40.8
53.3
63.6
72.5
91.1
98.2
Australia
11.3
12.1
11.2
10.8
11.3
14.9
17.0
18.7
19.1
22.8
27.1
Korea
39.3
45.5
56.3
50.4
54.9
64.4
78.7
91.9
103.4
116.7
133.2
Singapore
6.3
8.5
9.5
9.4
12.5
16.1
20.0
22.0
25.8
28.9
31.6
Taiwan
21.9
23.7
29.2
26.8
28.4
34.3
44.5
49.5
53.8
57.4
62.9
Other Asia/Pacific
24.8
29.1
30.9
30.8
33.3
38.8
45.5
52.9
62.9
72.2
90.8
Asia/Pacific
409.0
462.3
515.7
479.7
497.7
587.8
707.5
818.8
917.3
1041.0 1291.2
1573.5 1625.5 1719.0 1670.9 1748.8 2008.5 2325.6 2596.4 2858.1 3160.7 3696.8
Just as companies emerge as the main producers of the chemical industry, we can also look on a more global scale to
how industrialized countries rank, with regards to the billions of dollars worth of production a country or region
could export. Though the business of chemistry is worldwide in scope, the bulk of the worlds $3.7 trillion chemical
output is accounted for by only a handful of industrialized nations. The United States alone produced $689 billion,
18.6 percent of the total world chemical output in 2008.[2]
References
[1] "INEOS_Gassmaks09_Trondheim_Final" (http:/ / www. forskningsradet. no/ servlet/ Satellite?blobcol=urldata& blobheader=application/
pdf& blobheadername1=Content-Disposition:& blobheadervalue1=+ attachment;+
filename=INEOSSteinarKvisleGassmaks09TrondheimFinal. pdf& blobkey=id& blobtable=MungoBlobs& blobwhere=1243463935690&
ssbinary=true). . Retrieved 2009-06-06.
[2] Global (http:/ / www. americanchemistry. com/ s_acc/ sec_directory. asp?CID=292& DID=747)
Fred Aftalion A History of the International Chemical Industry. University of Pennsylvania Press. 1991. online
version (http://www.questia.com/PM.qst?a=o&d=10894619)
E. N. Brandt. Growth Company: Dow Chemical's First Century. Michigan State University Press. xxii+ 650 pp.
Appendices, Select bibliography and index. ISBN 0-87013-426-4. online review (http://eh.net/bookreviews/
library/0207.shtml)
Alfred D. Chandler. Shaping the Industrial Century: The Remarkable Story of the Evolution of the Modern
Chemical and Pharmaceutical Industries. Harvard University Press, 2005. 366 pp.ISBN 0-674-01720-X.
chapters 3-6 deal with DuPont, Dow Chemicals, Monsanto, American Cyanamid, Union Carbide, and Allied in
USA; and European chemical producers, Bayer, Farben, and ICI.
Chemical industry
Micheal McCoy, et al., "Facts & Figures of the Chemical Industry", Chemical & Engineering News, 84(29), July
10, 2006, pp.3572.
Shreve, R. Norris, and Joseph A. Brink Jr. The Chemical Process Industries. 4th ed. New York: McGraw Hill,
1977.
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License
License
Creative Commons Attribution-Share Alike 3.0 Unported
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