Chemical Elements

Periodic Table of Elements
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The Periodic System

Classification not only makes possible the systematic description of objects and phenomena but also points out the directions in which investigation may lead to new facts of moment. Hence classification is a necessary and very important factor in the development of a science. Soon after the advancement of the atomic theory by Dalton, began to develop the idea that not all atoms could be entirely unlike but that atoms of one element might have properties somewhat similar to those of some other element. With the increase in number of the known elements through new discoveries, more interest in the problem of their classification developed. As a result many arrangements were proposed. Early Classification: Many attempts were made to classify the elements on the basis of various properties, such as the acidic or basic characteristics of their oxides, or their valence, or their metallic and nonmetallic qualities. 1. Basic and acidic oxides: Almost coincident with the development of a fairly clear distinction between acids and bases, the elements were separated into two large groups, according to whether their oxides produced acids or bases with water. These groups contained acidforming and base-forming elements respectively. In this system a number of elements occur in both groups. For instance, manganese finds a place in each division because it yields a basic oxide, MnO, and an acidic oxide, Mn2O7. Furthermore, some oxides do not combine with water. Thus this broad classification is inadequate.
2. Valence: In spite of being considered as an classification property, valence is too much inconstant to be the basis of any systematic arrangement of the elements. 2. Metallic and nonmetallic elements: If an element in its solid or liquid state neither has a metallic luster nor conducts electricity, it is certainly a nonmetal; if it as the luster and is a conductor, it may be either a metal or a nonmetal. Because of a lack of agreement of physical properties, a consideration of chemical properties in classifying the elements into metals and nonmetals is in order. Typical metals lose electrons to form positive ions while nonmetals gain electrons to form negative ions. However, while some metals such as chromium and manganese act as expected in the formation of certain compounds, they may also constitute a part of negative ions! Thus no perfectly sharp distinction can be made between metallic and nonmetallic elements on this basis.
Classification based on Atomic Weight: According to the present point of view the atomic number is a more fundamental characteristic of an atom than its atomic weight. A value for the latter ism with a few exceptions, merely an average of the atomic masses of the isotopes of an element, and may be altered by various processes used to change isotopic ratios. However, an atomic number is an inalterable value and thus it represents a really fundamental property of an atom. 1. Dobereiner's Triads: In 1829, Dbereiner called attention for the first time to the suggestive relation between the atomic weights and the properties of elements. He pointed out that, from
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the elements, sets of three similar elements could be chosen having atomic weights such that the atomic weight of the central member is the mean of the other two. Such groups of three elements he called triads. Example of this are: Chlorine Bromine Iodine 35,457 79,916 126,92
Where the arithmetical mean of the atomic weights of chlorine and iodine is 81,19 2. Classification of DeChancourtois : This French engineer and geologist may in some measure be regarded as the first to devise a comprehensive scheme of classification based on atomic weights. His work was rather obscure and contained a number of arbitrary assumptions which prevented its general acceptance. However, the idea of periodicity was clearly indicated in this scheme. 3. Law of Octaves: In 1864 Newlands observed that if the known elements (beginning with lithium, for example) are arranged in the order of their atomic weights, the eighth element (in this case sodium) has properties closely related to the first. Of this relation, which he termed the law of octaves, he said; "The eighth element starting from a given one is a kind of repetition of the first, like the eighth note of an octave of music". Newlands was ridiculed in a meeting of the Chemical Society of London. Later however, the importance of the law was recognized.
Classification of Mendeleev
In 1869 the distinguished Russian chemist Mendeleev, apparently unaware of the work of Newlands, discovered an important relation between the atomic weights of the elements and their other properties, both physical and chemical. He developed the whole conception in so masterly a way and so thoroughly that his classification, with some modifications, persists to the present time. Almost simultaneously and quite independently the German chemist Lothar Meyer made similar proposals as to the relation between the properties of the elements and their atomic weights. To accomplish regularity, Mendeleev had to admit that the atomic weight of some elements was not correct. To keep the idea of periodicity, the position of some elements did not correspond to the predicted according to the atomic weight obtained by the chemists by the Canizzaro method. Mendeleev assumed that the position of some of the elements had to be changed. For instance, tellurium should be positioned before iodine in spite of having an atomic weight of 128 against the 127 of iodine. He also pointed out the exchange of elements like argon and potassium, cobalt and nickel or thorium and protactinium. When Mendeleev proposed the periodic table, some of the elements were not yet discovered, so he left its position free. It is the case of the elements similar to aluminum and silicon but with atomic weights of 65 and 75. These elements were later discovered and named gallium and germanium, respectively. Mendeleev predictions were all verified. It was later verified that yttrium, indium, dysprosium, cerium, erbium, lanthanum, thorium and uranium had atomic weight miscalculated. On the other hand, all the missing elements in the periodic table of Mendeleev were discovered. In the modern periodic table of Mendeleev, usually called the Periodic Table, each element has an order number, named atomic number and representing the number of electrons of the neutral atom which is equal to the number of nuclear protons.
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Further Reading a) "The Evolution of the Periodic System", Eric R. Scerri, Scientific American, Sept. 1998, pp 5661
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1. Hydrogen
It's not easy to place hydrogen in the Periodic Table since it does not fit in any of the existing groups. Sometimes it is placed in the top of the group I (alkali metals) due to its relatively electropositive nature. On the other hand, it is not dificult to realize that its behaviour resembles that of halogens, accepting a second electron and becoming a mononegative ion. In fact, the atomic structure of hydrogen (a nucleus with positive unitary electric charge and a single electron) is quite different from that of any other element, justifying its special place at the Periodic Table, not associated with any particular group. History: The nature of hydrogen began to emerge around the 16th century when F. B. Paracelsus first described a gaseous product arising when iron was dissolved in sulfuric acid. He described this product as "an air which bursts forth like the wind". Van Helmot described this gas as a special kind of air, which was combustible but could not support combustion. However, his ideas were quite fuzzy, since he confused hydrogen with other gases that could not also support combustion like methane or carbon dioxide. Priestley, and in general all the authors until 1783, used the term inflammable air to describe this gas as to hidrocarbons, hydrogen sulphite, carbon monoxide and other combustible gases. H. Cavendish (1766) showed that the inflammable air produced by the acid action on metals like iron, zinc or tin was a distinct and well defined substance. A. L. Lavoisier (1783) called this substance "hydrogen". Occurrence: Gaseous hydrogen occurs in Nature in relatively small amounts. The earth's atmosphere contains about one part of hydrogen per 15000 to 20000 of air (in molecules number), although this proportion increases with altitude. The gases emited by volcanoes, charcoal mines and oil wells contain hydrogen. Hydrogen is the most abundant element in the Universe. It is the main stellar and interstellar constituent. In the beginning of the 20th century, spectroscopical observations revealed the presence of hydogen in several nebula as well as in the sun's photosphere and chromosphere. Hydrogen frequently appears combined with other elements. With oxygen it forms water, the most abundant substance in the earth's surface and principal constituent of animal and vegetal tissues. The elements oxygen, hydrogen and carbon are the base of all organic molecules. Istopos: Three isotopes of hydrogen are known. The most abundant is protium (a single proton) followed by deuterium (a proton and a neutron) and the least abundant tritium, the third isotope which is very rare. Deuterium. In 1927 Aston obtained, through mass spectrometry, the value 1.00778 for the atomic mass of hydrogen. At the time, the agreement of this number with that obtained by chemists was thought to be enough not to think of any other hydrogen isotope. However, in 1929, it was put forward that the oxygen had three different isotopes with mass numbers 16, 17 and 18. Subsequent corrections to the atomic mass of oxygen induced some ajustments in that of hydrogen, obtained by chemical processes. A slight increase of this value made the scientists to think of a new isotope of mass number 2 and atomic mass 2.0147 with a 1 to 5000 proportion. Urey tried then to perform the separation of this isotope by fractionation of liquid hydrogen. The spectral analysis of the fractionation residue of huge amounts of hydrogen, revealed the existence of deuterium. Later, G. N. Lewis was able to isolate 1 ml of the so-called heavy water (D2O). The physical properties of this water were slightly different from ordinary water.
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Nowadays, deuterium has several aplications such as in NMR (Nuclear Magnetic Resonance Spectroscopy) or in the nuclear fusion process. Tritium. Tritium is the heaviest of the three hydrogen isotopes, with a nucleus having two neutrons and a proton. Tritium does not occur in Nature, since it is radioactive with a half-life of 12,3 years. However, tritium can be found around the Sun and probably through the space as a result of interstellar matter bombardment by cosmic rays. This isotope can be produced through the nuclear bombardment of deuterium by hydrogen, or through the reaction of thermal neutrons with lithium-6 in nuclear reactors. It is commercially available in the solution form. Tritium is mainly used as an hydrogen substitute in reactions, in order to study the process mechanisms or to identify and analyze products. This substitution makes the compounds radioactive (and heavier), making the monitoring of its presence and concentration an easier task, with radiation detectors. Orto and Para Hydrogen. Two atoms of hydrogen can combine to form a very stable hydrogen molecule. However, Heisenberg proved that, if we consider the nuclear spins, we can observe different "isomers". These isomers result from parallel or antiparallel coupling of the nuclear spins originating three or one quantic states respectively. At room temperature, these different quantic states have the same probability, but the spontaneous transitions between them are extremely rare and can be ignored. As a consequence, normal hydrogen behaves as a mixture of three (volumes) of orto hydrogen (parallel spins) with one (volume) of para hydrogen (antiparallel spins) For simmetry reasons, the rotational states allowed for the considered molecule differ in both cases, being the lowest energy state that of the para form.
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2. Helium
Helium has a characteristic and bright spectrum that easily identifies the element. Its bright yellow spectrum stripe, responsible for the discovery of the element, is not hiden by any other element. Scientifically, hellium is one of the most important elements. History: Hellium, the lighter of the noble gases, was the first to be discovered. In fact, this element was first identified in the Sun rather than in the Earth. In 1868, during a solar eclipse in India, a spectrometer was used for the first time in the study of the chromosphere around the Sun. The chromosphere's spectrum, among other bright stripes, contain the hydrogen characteristic stripes and a yellow one that, at the time, was thought to be corresponding to sodium. The French astronomer Janssen decided to study the origin of that stripe and tried to reproduce the chromosphere's spectrum starting from ordinary light. He succeeded his purpose proving that the yellow stripe did not belong to sodium, but was probably the stripe of a new element. Lockyer and Frankland confirmed Janssen's results and proved that the bright yellow stripe could not have an earthly origin. Frankland proposed the name "helium" after the Greek word "Helios" for Sun. This stripe was later detected in spectrums of many other stars and, in 1882, Palmieri observed it in gases erupting from Vesuvius. The search for this new element in the Earth was not very productive until 1895, when Sir William Ramsay examined a gas produced by a Norwegian ore (cleveite) when treated with acids. In this gas spectrum the bright yellow stripe appeared, proving the existence of hellium on Earth. Sir William Ramsay made this discovery after the work of Hillebrand, in 1888, that stated that the boiling of uraninite with diluted sulfuric acid produced considerable amounts of an inert gas. He proved that part of this gas was nitrogen, and since helium was not known at the time, he thought that it was only nitrogen. In a letter to Sir William Ramsay, after the discovery of the element, Hillebrand mentioned that he noticed some strange stripes not present in a pure nitrogen spectrum. He did not take this in to account, but only mentioned it to his assistant, loosing in this way the merit of the discovery. The discovery of hellium in radioactive materials was not totally understood until the discovery of radium in 1898. Then, it was verified that helium was a stable product of the radioactive elements desintegration. This led some scientists to conclude that the hellium present in Earth had that origin. Some others thought that the origin of helium on Earth was a survival of the "primordial helium". Occurrence: The discovery of helium was made in radioactive materials and for a while the element was thought to be very rare. However, a few years later, it was proved to be present both in the earth's crust and atmosphere. Accordingly to Ramsay, the atmosphere near the Earth contains 0.0004% of hellium (in number of molecules) i.e one hellium molecule per 200000 air constituents molecules. Helium was also found very low quantities in rocks, natural and vulcanic gases and radioactive minerals. Applications: Helium was initially used in dirigible-balloons. Nowadays, is used just like argon, in the production of an inert gaseous atmosphere during magnesium, aluminum and titanium welding; it can be used in the cooling of nuclear reactors as transfer media, since it is an inert gas. Hellium is also used, mixed with oxygen, in asthma treatment because it diffuses very easily through the lungs. It can also be used in respiratory mixtures for high depth divers, because it is less soluble in blood than nitrogen. In the liquid state, it is used to achieve extremelly low temperatures in electronic devices or for studies in the region of 0-5 K. Hellium is also the adequate gas for low temperature gas thermometers due to its low boiling point and almost ideal behavior.
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3. Lithium
History: Lithium was discovered in 1817 by Arfwedson when studying a mineral called petalite. However, he did not isolate the metal. The metal was first isolated in 1855 by Bunsen and Matthiessen in 1855, through the electrolysis of molten lithium chloride. Its name derives from the Greek word for stone, since it was believed that lithium was only present in the stones. Occurrence: Lithium does not occur free in Nature, and, even in compounds, is far away from being abundant. The element appears widely in the terrestrial crust with an estimated percentage of the order of 0,004%. The major source of lithium is spudomene, lepidolite, amblygonite, petalite and eucryptite, all of them lithium alumni-silicates. Lithium salts have also been detected in the ashes of many plants, namely tobacco, in the milk, blood or in mineral sources. Applications: It is used as a desgasifier and refining agent for molten metals and in the production of copper and its alloys. Also, it acts as a grain refinement agent and increases the fluidity of the molten metals. Due to its low atomic mass, lithium compounds are always present in relatively small molecular masses, giving advantages in certain applications, as in the use of lithium hydroxide in the carbon dioxide absorption in submarines and spacecrafts. The existence of small percentages of lithium oxide in some substances used in ceramic lowers sensibly the respective melting points. Lithium carbonate is used for this effect as well as in the production of special types of glass. The lithium fluoride is used in the manufacturing of prisms and infrared spectrophotometers and it is used in the production of enamels. The lithium chloride and bromide can be used as drying agents and are also used as lubricants. One of the most important applications of this element is in the reagent preparation for organic synthesis, in particular of the complex hydrides of aluminum and boron, with widespread applications. Biological action: Lithium is the more toxic of the alkaline metals. However, its effects can be neglected because the element does not have any important risk to human health. The excessive ingestion of lithium compounds should be avoided because they can cause nervous disturbs and dizziness. The ingestion of lithium chloride is recommended, in certain diets to substitute the traditional sodium chloride; even in these cases, it can originate dizziness, visual disturbances, and shivering or mental confusion. These symptoms dissuade the ingestion of these compounds, in spite of the fact that it is not cumulative. However, lithium compounds, in appropriate doses, are used in the treatment of maniac-depressive diseases. Lithium is not an indispensable element in the plant growth and there is no indication that it could play an important role in animal biology. The mentioned adverse effects are probably due to the disturbances caused by the lithium in sodium-potassium-calcium balance of the living cells.
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4. Beryllium
History: Vauquelin discovered beryllium in 1797 as a constituent of the mineral beryl. Aquamarine and emerald are the most popular varieties of this mineral. In the French language the element is referred to as glucinium. This name is derived from the sweetish taste of many of its compounds. The first metallic beryllium was produced by Wohler and Bussy in 1828. They obtained beryllium in the form of an impure powder by reducing beryllium chloride with metallic potassium. Of particular interest is the work of the French scientist Lebeau, published in 1899, which includes descriptions of the electrolysis of sodium-beryllium fluoride resulting in the production of small, hexagonal beryllium crystals, and the preparation of beryllium-copper alloys by direct reduction of beryllium oxide with carbon in the presence of copper. Also of interest is the work by the German scientist Oesterheld who, in 1916, published the equilibrium diagrams of beryllium with copper, aluminum, silver and iron. Ocurrence: There are some thirty recognized minerals containing beryllium; only three of them are significative, namely, beryl, phenacite and chrysoberyl. Of these three, only beryl is now of industrial importance. In pure form this mineral is a beryllium aluminum silicate present in emerald and aquamarine. Ocurrences of beryl in the earths crust are widely distributed and are estimated to amount to approximately 0.001%. However, beryl ore containing 10 to 12% beryllium oxide has not yet been found in large enough quantities to be mined economically. The supply is, therefore, generally obtained as a by-product of mining feldspar, lithium or mica. The principal producers of beryl ore are South Africa, Zimbabwe, Brazil, Argentina and India. Small amounts are produced in East Africa, Morocco, Mozambique, Portugal and Canada. Applications: The most important reasons for the development of beryllium metal as an industrial material has been its nuclear characteristics and hardness. Examples of applications based on this properties are block and heat shields, guidance systems parts, gyroscopes, stable platforms, accelerometers and mirrors (in this case beryllium is used as a rigid carrier for a highly polished surface). More sophisticated current applications of beryllium are shingles for cladding the capsule used in the Gemini program, the inner stage joining element for stages of the Minuteman missile, and skin panels for the Agena booster. Aerospacial applications have been one of the driving forces for the industrial production of beryllium. Beryllium oxide is unique among ceramic materials, since it combines an extremely high electrical resistivity and dielectric constant with a large thermal conductivity. The x-ray transparence of beryllium makes it useful in the manufacturing of windows for radiation detectors. The nuclear properties of beryllium oxide, combined with its high melting point (above 2000 C), makes it ideal for high-temperature reactor systems where other metal could melt and deform. The copper-beryllium alloy has a extremely high stiffness and elasticity. Biological Action: Under some circumstances beryllium dust, mist, fume or vapor, when inhaled, may be hazardous to health. In addition, the soluble beryllium salts may produce a dermatitis on contact with the skin. There is, however, no ingestion problem. The hazards are generally classified as an acute respiratory disease, a chronic disease or dermatitis. It is generally accepted that the acute disease is caused by exposure to airborne dust, mists, or fume of the soluble salts of beryllium, especially beryllium fluoride and sometimes the sulphate. The acute disease, which is similar to the conditions caused by exposure to phosgene, or oxides of nitrogen, has a relatively short latency period (a few days). The chronic disease is the more important industrial hazard met when working with beryllium, since it has a latency period with a remarkable variance. However, since 1949 there are no disabling cases of berylliosis. For people working with beryllium, preplacement and periodic medical examinations should be routine.
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Dermatitis is produced by skin contact with soluble salts of beryllium, especially the fluoride. Besides rash, irritation of the nose, throat and eyes is encountered. Granuloma may result from embedded particles in the skin. Dermatitis is controlled by a program of good personal hygiene, frequent washing of the exposed parts, as well as by a clothing program where clothing is laundered on the working plant site. This practice also keeps beryllium from going home with the worker, preventing henceforth non-ocupational exposures.
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5. Boron
History: Boron compounds may have been known for about 6000 years, starting with the Babylonians. The Egyptians, Chinese, Tibetans and Arabians are reported to have used such materials. The Arabs used the expression "baurach" for a number of minerals including the now familiar borax. Elemental boron was not known until the early nineteenth century when Sir Humphrey Davy, Gay-Lussac and Thenard prepared boron by reduction of boron trioxide with potassium and by electrolysis of moistened boric acid. The purity of their products was about 50%. Fifty years later impure boron products resembling both diamond and graphite were produced. The diamond-hard material was found to be largely aluminum boride (AlB12), while the graphite variety was a complex boron-aluminum-carbide. Much later, a higher purity boron was made by reduction of boron trioxide with magnesium. Purities of about 90% can be achieved by this procedure. The product is light boron in color and is considered to be amorphous. Boron did not become of interest until the twentieth century when it was found that it formed many unusual and complex compounds. It has been during the last forty years that the right physical and chemical properties have been determined. High purity boron produced by electrolysis and vapor deposition methods have made such determinations possible. Occurrence: Boron is sufficiently reactive to preclude its occurrence in the free state.the sources of combined boron are sassolite (H3BO3), found in Italy; colemanite (Ca2B6O11.5H2O); ulexite (CaNaB5O9.8H2O); and kernite (rasorite, Na2B4O7.4H2O), in the United States. Ulexite is also found in Bolivia, Chile and Peru. Boracite (Mg7B10Cl2O30), is found in Germany. The world's major source of boron is kernite from the Mojave Desert in California, USA. Applications: Boron in its combined form of borax (Na2B4O7.10H2O) has been used since early times. Early uses were as a mild antiseptic and cleaner because of its detergent and watersoftening properties. Later it was used as a soldering flux and ceramic flux because of its ability to dissolve metal oxides. Borax is used to produce a heat-resistant borosilicate glass for the home and laboratory, familiar to many by the trade mark "Pyrex", and is the starting material for the preparation of other boron compounds. Boric acid, is mildly antiseptic, is used widely as an eye washer and as a neutron absorver in the swimming-pool type nuclear reactors and in electroplating baths, such as those used for nickel deposition. Its anhydride is used as a source of boron in the fused salt electrolysis method for the preparation of elemental boron. The boron trifluoride is a gas produced in large quantities for gas tube neutron radiation detectors for monitoring radiation levels in the earth's atmosphere and in space. Some organizations use these devices to ascertain the best underground level at which to blast to produce oil wells of high yield. Boron triflouride is an important industrial catalyst for many organic reactions, such as polymerization reactions. It has also a major role in the electroplating of nickel, lead and tin. Aluminum boride (AlB12), has been used as a substitute for diamond dust for grinding and polishing. Boron carbide is also used with this purpose and it has found extensive use as a polishing agent, for sandblast nozzles, etc. Elemental boron is hard and brittle like glass, having similar uses. Boron can be added to pure metals, alloys or to other solids to improve its strength. Biological Action: Boron in the elemental form is not toxic. The finely divided powder is hard and abrasive, and may cause skin problems indirectly if the skin is rubbed after contact. Trace amounts of boron seem necessary for good growth of plant lie, but large amounts are toxic. Boron accumulated in the body through absorption, ingestion and inhalation of its compounds affects the central nervous system. The symptoms are depression of circulation, vomiting and diarrhea, followed by shock, coma and a body rash.
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6. Carbon
Carbon is unique among the elements because it forms a vast number of compounds, more than the total of all other elements combined with the exception of hydrogen. It exists in three allotropic forms, namely, diamond, graphite and amorphous carbon. Recently new carbon molecules such as C-60 were discovered. The C-60 shape is an example of a new class of substances called fulerenes. Diamond and graphite are naturally occurring crystalline solids with widely divergent properties, whereas amorphous carbon is a term applied to a comparatively large variety of carbonaceous substances not classified as either diamond or graphite. History: Carbon is of prehistoric knowledge as diamond as well as graphite. That diamonds were known at least as early as 1200 B.C. seems probable according to ancient Hindu writings. The earliest authentic reference to the diamond is ascribed to one Manilius near the First Century of our era. The name diamond derives from a corruption of the Greek word adamas "the invincible". The first recognition of graphite is obscured in antiquity. It was confused with other minerals of similar appearance, chiefly molydenite (MoS2). One name for graphite is plumbago, like lead; and until modern times it was thought to contain lead. Scheele, in 1779, demonstrated that graphite oxidized to carbon dioxide providing its chemical constitution. The name graphite, which comes from the Greek verb graphein, "to write", originated with Werner in 1789. Carbon as a reduction agent in the making of iron and other metals is also of prehistoric origin. Not until modern times, however, was the identity and role of carbon in such processes established and completely understood. Prevalence: Carbon ranks nineteenth in the order of abundance of the elements comprising about 0.2% of the earth's outer crust. In the earth's atmosphere carbon is present as carbon dioxide in amounts up to 0.03% by volume. Though it is widely distributed in Nature, mainly in the combined form, only minor amounts are found in the free or elemental state. It is present as main constituent of all animal and vegetable matter. Coal, petroleum and natural gas are also composed essentially of carbon. Various minerals, such as limestone, dolomite, and marble as well as certain marine deposits such as oyster shells all contain carbon in the form of carbonates. Carbon plays a vital role in the so-called carbon life cycle. Carbon dioxide from the air, together with water, is absorved by plants and converted into carbohydrates in the process of photosynthesis. Animals consume the carbohydrates, returning the carbon dioxide to the atmosphere by the processes of respiration, excretion, fermentation and decay under bacterial action. Diamond. Diamond is the only precious stone composed of a single element. Though diamonds have been discovered on all the major continents, over 90% of the world's natural diamond production comes from Africa. Other significant producers are Russia (mainly Siberia), China, Brazil and Angola. In the United States, diamonds can be found in the states of Arkansas, Virginia, Wisconsin and California. India, that was the only producer before the XVIII century, has a very small production nowadays. Diamond crystals can also be found in meteorites. In spite of the first attempt of the Scottish chemist J. Balentine Hannay, in 1880, to produce artificial diamond it was not until 1955 that the General Electric Company first announced the successful development of a reproducible process. The work of Francis Bundy, Tracy Hall, Herbert M. Strong and Robert H. Wentorf complemented the research by Percy W. Bridgman from the University of Harvard. This diamonds have industrial quality being nowadays produced by an identical method, in large scale. Precious-stone quality crystals were obtained in 1970 by Strong and Wentorf in a process involving extremely high pressures and temperatures.
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In spite of the popular interest on diamonds based on its value as gems, it is on the industrial domain that diamonds play a major role. They can be used in cutting or in turnery and to pierce alumina, quartz, glass and ceramics. Diamond powder is used to polish steel and alloys. Graphite. Graphite crystals consist of superposed layers of carbon atoms, in an infinite net of hexagonal cycles. The free space between the layers can be occupied by several distint atoms, molecules or ions (oxygen, nitrogen, halogen, alkaly metals etc.), thus producing lamellar compounds. In normal conditions of pressure, the graphite layers easily glide due to the very weak bounds with the vicinity (van der Waals bonding); this is the reason why graphite is used as a lubricant. Graphite occurs mainly in Corea, Austria, Russia, China, Mexico, Madagascar, Germany, Sri Lanka and Norway. However, most of the graphite used nowadays has a synthetic origin. Thanks to its infusibility, hardness and conducting power, this substance is mainly used in the production of refractory coatings and crucibles in the foundry industry. It is also used in the production of pencils, electrodes for multiples purposes, rotary brushes, lubricants corrosion-resistent paints. Applications: Carbon is an indipensable element in industry. By far, the greatest single use of carbon is in the form of coke for the iron and steel industry. The major portion of this coke is used in the reduction of iron ore in blast furnaces. As in the rubber industry, the major applications for carbon blacks are in the printing ink, paint, paper and plastic industries. Minor amounts are used in the manufacture of dry cells and carbon brushes, and as insulation. The largest single application for gas phase activated carbons is in the recovery of volatile organic solvents from air or vapor mixtures. Another large application is in the purification and separation of natural and industrial gases. Main applications for pyrographite and the fiber forms of manufactured graphite are found as components for rockets, missile and other aerospace vehicles. Biological Action: No toxic effects appear to be associated with carbon in its elemental form. On the other hand, many of the more commom carbon compounds exhibit strong toxicological effects. Principal among these are carbon monoxide, carbon dioxide, hydrogen cyanide and the alkali cyanides, carbon tetrachloride and carbon disulfide. Carbon monoxide, an odorless gas, is extremely toxic, behaving as an asphyxiant. Compared to oxygen, it is not only more readily absorved, but also more firmly bound by the hemoglobin of the blood. The capacity of the blood to carry oxygen to the vital parts of the body is thereby reduced, leading to brain damage, heart disease and pneumonia. Carbon dioxide is less toxic and behaves chiefly as a simple asphyxiant and narcotic. Hydrogen cyanide and the alkali cyanides are extremely toxic, functioning as protoplasmic poisons by inhibiting tissue oxidation. Acute exposure to the vapors of carbon tetrachloride can result in damage to both the liver and kidneys. Carbon disulfide is a powerful narcotic, but its chronic effects are more serious. Excessive exposure can lead to permanent damage to the nervous system.
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7. Nitrogen
History: Nitrogen was independently discovered, in 1772, by Daniel Rutherford and Priestley. Later, it received from Lavoisier (1775-1776) the name "azoe", and from Chaptal (1790) the one of "nitrogen". There are innumerous compounds of this element, in the domains of the organic and inorganic chemistry. Among the last ones the following are especially important: binary compounds (nitrogen and hydrogen, oxygen, halogens and metals); nitrogen oxacids and corresponding salts; hydrocyanic acid, cyanides, etc. Among the binary nitrogen and hydrogen compounds, the ammonia, the hydrazine and hydrazoic acid, have special relevance. The most important is ammonia. Excellent solvent when liquefied, it is, on the other hand, an excellent ionizing media. Occurrence: The nitrogen concentration in the atmosphere is about 78,03%, being therefore the air the main commercial source of this element. After liquefaction, air is proceeded to a set of fractional distillations to separate the several components, among which nitrogen is present. Wrobliski and Olzewski liquefied this elementary substance for the first time in 1883. Nitrogen can also be produced through the combustion of carbon or hydrocarbons of the air, extracting carbon dioxide and water from the gaseous products through appropriate techniques. Applications: Gaseous nitrogen has a wide variety of industrial applications, with special relevance to the chemical, alimentary, electrical and metallurgical industries. In the chemical industry, it is used to dilute reagent gases, to increase the yield of some reactions, to decrease the fire or explosion risk of some other reactions or, still, to avoid the oxidation, decomposition or reagent or products hydrolysis. In the food industry it is frequently used to avoid the oxidation of certain wastes or still to inhibit mildew and insect development. In the electrical industry, the nitrogen is used to avoid oxidation's and undesirable chemical reactions. It can also be used in the pressurizing of the electrical cable coatings, in lasers and as motors shielding. In the metallurgical industry it is used in great amounts to avoid the oxidation of certain metals or the carbonization in the welding processes. Nitrogen is still used as non-reactive gas in production of rubbers or expanded plastics, also with application in wind tunnels or as pressurizing liquid of reactor propellers. The uses of the liquid nitrogen are related with its availability, chemical inertia and lower temperature. The transport industries related with the alimentary sector use liquid nitrogen in refrigeration and freezing systems. With this process one can assure the original texture and the natural flavor of food. Liquid nitrogen is also used in cryobiology to preserve blood, bone medulla, organs and semen. In the electronic industry the liquid nitrogen is used in the refrigeration of electronic components. Biological Action: The biochemistry of nitrogen compounds foreshadows the complex analysis of protein chemistry. Generally there are three great classes of proteins: the proteins that occur naturally (albumin, globulin, protamins etc.), the conjugated proteins, that is, combinations of proteins with other substances (nucleoproteins, glycoproteins, phosphoproteins, chromoproteins or lipoproteins); and the derived proteins, formed from the hydrolysis of a protein molecule (metaproteins, peptone, coagulated proteins etc.). Some enzymes contain also nitrogen. The "nitrogen fixation" is the name of any process where the free nitrogen combines with other elements, originating the nitrogen compounds. This "fixation" can be made chemically or through certain bacteria, as the azotobacter chroococcum and clostridium pasteurianum. In the natural processes of "nitrogen fixation" there are a cooperative action between bacteria and certain plants as the peas, the beans or the clover. The nitrogen cycle foreshadows that the animals obtain the nitrogen through the ingestion of proteins, either animal or vegetable. The plants synthesize its proteins from the inorganic compositions of the soil. They can also absorb free nitrogen from atmosphere through some existent bacteria in the soils.
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When the animals are exposed to high atmospheric pressures, there is a considerable portion of nitrogen that is dissolved in the blood or in another fluids of the body. If the pressure decreases drastically, the nitrogen dissolved form small bubbles, that wandering freely in the corporal liquids can cause paralyses, fainting, pains in muscles and articulations and, eventually, death. These symptoms can be avoided with a slow decompression. In the living organisms, the usual concentration of nitrogen is 16%, while its natural abundance is of about 0,3 parts in 1000.
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8. Oxygen
History: According to Duckworth, that obtained this information in an old book of chemistry of Klaproth, 13th century Chinese already knew the composition of water and, in a certain way, the nature of the atmosphere. They knew that the air had more than a constituent and that the element, now called oxygen, tended to bond with many metals, sulfur and carbon, but not with gold. According to them, the oxygen could be prepared by heating up saltpeter (potassium nitrate) and certain minerals like pyrolusite (manganese dioxide). Besides, they also recognized that the oxygen was one of the constituents of water. The role of the air in the combustion was observed by Leonard da Vinci (1452-1519) and in 1669 by Mayow who stated that the spiritus nitro-aereus (oxygen) caused a mass increase in the metals when heated up. Determining the oxygen content in the air, he proved that it was consumed during the combustion and during the breathing of the animals, and that the two processes had the same purpose. In 1678 the oxygen was extracted from saltpeter by Borch; in 1731, from the same substance by Hales; and in 1774 from the mercury oxide by Bayen. In August 1, 1774, about five months after the preparation of the gas oxygen by Bayen, Priestley obtained this gas focusing sunrays in red mercury oxide, using for that two lenses, one with 16 and the other with 7 inches of diameter and separated by 16 inches. Its interest increased when he introduced a lit candle in the gas, that burned with "an extremely vigorous" flame. He called the substance "deflogisticated air", not recognizing the true composition of the gas. Between 1771 and 1773, the Swedish chemist Scheele prepared oxygen from nitrates and through other methods, discovering many of its properties, and its capacity to combine with the metals and with phosphor. Its results, however, were only published in 1777. However, neither Priestley nor Scheele were able to know the true nature of this element, expressing their theories based in the almost dogmatic doctrine of the "flogisto". This work was reserved to Lavoisier. The great French chemist was studying combustion and breathing. He was interested in the oxygen and recognized the role of the element in the calcination processes, combustion and breathing. Lavoisier succeeded in describing oxygen because, unlike its contemporaries, just based his work on experimental facts, establishing the chemical science, for the first time, in a purely quantitative base. This was his great contribution to Chemistry and he is frequently referred to as the father of the modern Chemistry. In agreement with his observations, some elements as the sulfur and the phosphorus burn in the oxygen forming compounds that at the time were considered acids. He concluded, although improperly, that oxygen was the fundamental constituent of all the acids and gave its actual name, which in Greek means "producing of acids". Occurrence: Oxygen occurs as an elementary substance in two allotropic varieties: the natural oxygen (second constituent of the air) and the ozone. It also forms a great variety of compounds and, in the combined state, it is the most abundant element of the terrestrial crust (in the silica and silicates form) and of the oceans (in water). Oxygen reacts with some complex transition metals which act as transporters of the substance, i.e., they capture and give O2 in a reversible way. Some of these complex metals constitute prosthetic groups of indispensable proteins to the metabolic process of breathing. That is the case of the hemoglobin and of certain hemocyamines that are natural carriers of oxygen. Applications: Oxygen is mainly used in the metal-mechanic industries for welding and casting materials made iron and steel; it is also used in the production of synthesis gases, for oxidation of the natural gas and for reduction of the water vapor by the carbon. It is also used in the production of a great variety of substances of industrial interest, as the acetylene, the hydrogen peroxide (oxygenated water), the chlorine (for oxidation of HCl), the ethylene oxide, the ftalic anhydride, the ozone, etc. Less usual applications include the gas in bottles used by divers, in hyperbaric chambers for therapeutic purposes and in reaction motors.
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Biological Action: Oxygen plays a vital role in the breathing processes and in the metabolism of the living organisms. Probably, the only living cells that do not need oxygen are some anaerobic bacteria that obtain energy from other metabolic processes. In the human body, the oxygen is absorbed by the blood stream in the lungs, being then transported to the cells where an elaborated change process takes place. The nutrient compounds, inside of the cell, are oxidized through complex enzymatic processes. This oxidation is the source of energy of most of the animals, mainly of mammals. The products are carbon dioxide and water, which are eliminated by the body through the lungs. The oxygen is useful in the treatment of pneumonia, emphysema, some heart disturbances, and another diseases. Sometimes hyperbaric oxygen chambers are used to treat poisoning victims by carbon monoxide or by anaerobic bacteria in the breathing system. The oxygen can increase the effects of the radiation in the cancerous cells, so that this treatment should be made in hyperbaric oxygen chambers. The use of atmospheres extremely rich in oxygen increases the fire risk, so rigorous precautions should be taken in these conditions.
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9. Fluorine
History: The fluorine compounds are very common and well known for a long time, but it was only in 1886 that a method was discovered to remove electrons to fluorine ions in order to produce elemental fluorine. In 1860, Gore was able to produce small amounts of fluorine gas, but with a very arcaic method. It was Henri Moissan, in 1886, the first to isolate the element by electrolysis of a mixture of fluoridric acid with potassium fluoride and hydrogen. The name fluorine derives from the latim fluo (that runs), because of the use of calcium fluoride as dissolvent. Occurrence: Fluorine is widely distributed in the earth's crust. Despite this, fluorine does not commonly occur in deposits sufficiently rich for commercial development and only three minerals are important, namely, cryolite (3NaFAlF3), fluorspar (CaF2) and fluorapatite (CaF2 3Ca3 (PO4)2 ). Cryolite or Greenland spar is not a common mineral and commercial deposits occur only in Greenland. Cryolite has numerous industrial applications, the most important being in the aluminum industry, and it is now manufactured synthetically from fluorspar. Fluorspar is the most important fluorine mineral in commerce. Its workable deposits are found in many such as the United States, Mexico, ex-URSS, China and Europe. The principal uses of fluorspar are in the steel industry, in the manufacture of hydrofluoric acid and cryolite, and in the ceramics industry. In contrast to the high flourine content of fluorspar, fluorapatite has only 3.5% of fluorine. It occurs in massive form as phoshate rock deposits in the United States, ex-URSS, North Africa and islands of the Pacific and West Indies. It is used by the phosphate fertilizer industry. Applications: Until the beginning of World War II there was not any commercial production of fluorine. It was only the development of new nuclear reactors that brought up the need for producing fluorine. The technical progress allow nowadays the store and transport of fluorine quantities in an absolute secure way. Fluorine is used in the preparation of organic compounds containing fluorine used in the production of hard plastics resistant to high temperatures (teflon), pharmacological products, toothpastes, cooling fluids and aerosol products (freon). It is also possible to use fluorine in rocket propulsion. Biological Action: Fluorine is a highly toxic gas, for which the recommended maximum allowable concentration for a daily 8 hour exposure is 0.1 ppm. It can, in fact, be detected by its smell in a concentration of 3ppm, while an atmosphere containing 50 ppm is intolerable. The inhalation of high concentration of fluorine causes asphyxia and subsequently would results in severe lung congestion. High fluorine concentrations on the skin produce thermal burns. All inorganic flourides that have an appreciable solubility in water are toxic when ingested in quite small amounts. Less than 1 g of sodium fluoride is a fatal dose. It is now well established that drinking waters must contain about 1 ppm to reduce dental caries, but in quantities superior to 2 ppm can be prejudicial to oral health. Usually, the fluorine is supplied by the public water distribution so its composition must be tightly observed.
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10. Neon
History: Neon was discovered in 1898, by Ramsay and Travers. These scientists suspected that there was a missing element in the family of the previously discovered noble gases that could justify a serious research. The fractional distillation of liquid air produced a rich mixture in helium and in other gas that was called "neon" (from the Greek "new"). The remaining oxygen and nitrogen traces were removed by chemical processes, and the neon was frozen using liquid hydrogen. At this temperature, the helium remained in the gaseous state and it was removed of the solid neon. About 44 tons of liquid air are necessary to obtain a pound of neon. The element is chemically inert, as well as the other members of this group. Occurrence: Neon is widely distributed in the entire Universe. The thermonuclear reactions between carbon and oxygen, that occur in the stars cores and are responsible for its high temperatures, can eventually create neon. Some of these stars explode, originating novas or supernovas, releasing huge amounts of gas, responsible for the existence of neon in clouds of interstellar gas. Probably, neon was part of the condensing material that originated the Earth, being later freed to the atmosphere by the erosion of the rocks in the crust. However, most of the neon that occurs in the Earth refers to its formation period. Applications: The more important application of this substance is in the filling of tubes for luminous advertises (neon tubes). These tubes consist in a neon and helium or argon lowpressure mixture submitted to electrical discharges. The color of the emitted light depends on the composition of the gaseous mixture and of the color of the glass of the tube; with pure neon and colorless tubes we can obtain a red light and with the mixtures above referred we can see a blue shine. The neon is also used in fluorescent lamps, warming lamps for electronic equipment, stroboscopic lamps for motion control of machines, as a filling gas of Geiger-Muller counters, in scintilators and ionization cameras and other devices for radiation detection. It is also used in the production of lasers of this gas, in a pure state or mixed with helium.
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11. Sodium
History: The sodium chloride, the common kitchen salt, and the sodium carbonate are known since Antiquity. The first is probably a vital need and it was probably used in the food since immemorial times, while the second, besides occurring naturally, constitutes a considerable portion of the ashes of marine algae, being already known and used by the ancient Egyptian. Metallic sodium was first isolated by Sir Humphrey Davy in 1807 using the electrolysis of solid sodium hydroxide. At that time, sodium and potassium hidroxides were considered elementary substances and were called fixed alkalis. Davy also obtained metallic potassium; in a letter to a friend, he wrote concerning its discovery: "I decomposed and I recomposed the fixed alkalis and discovered that its bases were two new very inflammable substances similar to metals; but one of them is lighter than the other and very reactive. There are like this two decomposed bodies and two new discovered elementary bodies". Occurrence: Sodium chloride exists in the ocean water in enormous amounts, occurring equally in great halite deposits, formed by the evaporation of prehistoric seas, or still in dry salted lakebeds. The main deposits can be found in the USA, United Kingdom, France, Germany, China and India. In a lot of regions, like Portugal, the evaporation of the sea water is the used extraction process. The sodium also occurs in several ores, like borax, the cryollite and the Chile nitrate. Applications: Sodium can reduce many oxides of other metals and it is often used as reducing agent, just as its hidride. It forms alloys with many metals, with special relevance to lead and mercury. From the reaction with several organic substances inumerous derivates result as well as free radicals, many of them important used in organic synthesis, like polymerization reactions. The more important sodium compounds are the chloride, the hydroxide, the peroxide, the tripolyphosphate, the tetraborate, the silicates, the chlorate, the tiossulfate. The sodium chloride constitutes the main raw material in the obtaining process of the other salts; the hydroxide is used as industrial reagent, in the production of soaps, cellulose, paper, rayon, and many other products; the peroxide is an oxidizer agent used as bleach of textile fibers; the tripolyphosphate is used in water treatment; the tetraborate is used in the production of detergents; the silicates are used in the production of glasses; and the chlorate in the production of explosive; finally, the tiossulfate is used in photography as a developer. Biological Action: Sodium is an essential biological element to the more advanced animals; the ratio sodium/potassium concentrations in intercellular and extracellular fluids is responsible for the transport ions through the cellular membranes, the regulation of the osmotic pressure inside the cell, the transmission of nervous pulses and other electrophisiological functions. Since there no reserve store of sodium ions in the animal body, losses above the amount of intake come from the functional supply of cells and tissues. This depletion results in serious symptoms and even death. Thus, the importance of NaCl in nutrition has been recognized since prehistoric times. Human populations living on grains, vegetables and fruits experience a salt hunger that causes them to got to great lengths to obtain salt. Sodium deficiency may result from extreme excretion of sodium ion by sweating and other loss of body fluids. It is evidenced by thirst, anorexia and nausea. Other results of severe sodium loss are lassitude, muscle cramps and mental disturbances.
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12. Magnesium
History: In 1695, Nehemia Grew published an article describing salts found in water of mineral sources in Epsom, United Kingdom. The medicinal properties of this salt attracted some attention; in England these salts were called Epsom salts and in the continent salt anglicum. The magnesia alba (magnesium carbonate) was already commercialized in Rome about 1700; the term magnesia alba was used in contrast with magnesia nigra, the black manganese oxide. In 1755, J. Black clearly distinguished magnesia from lime, showing that the first tend to form a soluble sulfate and the latter tend to produce an insoluble one. In 1808, Sir Humphrey Davy isolated the metal (not pure) and called it "magnium". At the time, the terms "magnesium" and "manganese" were used to denominate the manganese, obtained from the mineral pyrolusite (manganese dioxide) and the name magnesium to denominate the magnesia alba. To avoid confusions, the term "magnesium" is used refering to the existent element in the magnesia alba and "manganese" for the existent element in the pyrolusite. Occurrence: Magnesium is abundant in Nature mainly in seawater as positive ion, and in the terrestrial crust in the magnesite form (MgCO3), dolomite (CaCO3 MgCO3) and many common silicates, as asbestos (H4Mg3Si2O9), talc (Mg3 (Si4O10)(OH)2) and olivine ((Mg,Fe)2SiO4). The element also occurs as brucite (Mg(OH)2) carnalite (KCl.MgCl2.6H2O) and kieserite (MgSO4.H2O). Applications: Among other applications of its compounds we can point out the use of the magnesium oxide in the production of refractory materials and in the rubber, fertilizers and plastics industries, the use of the hydroxide in medicine as antacid and laxative, the use of the carbonate as insulating material in boilers and tubage, and still in the rubber, cosmetics and pharmaceutical industries. The sulfates (Epsom salts) are used as laxatives, fertilizers for poor magnesium soils and still in the textile and paper industries; the chloride is used in the production of the metal, in the textile industry and in the manufacture of glues and special cements. Among the organic compounds of magnesium we refer the reagents of Grignard used in organic synthesis and, in large scale, in the silicones production. Special reference must be made to chlorophyll which plays a fundamental role in the metabolism of the plants. The metal applications are multiple and diverse. Special emphasis must be taken in the mechanical construction in the aeronautics and automobile industries, used as pure metal or in alloys with aluminum and zinc, or with less usual metals, as zirconium, thorium, lanthanides and others. It is still used in explosives production, in pyrotechnics, in the production of organic or organometalic compounds, in the production of light batteries and of anticorrosion devices, in the production of the beryl, titanium, hafnium, zirconium, uranium and other metals, in the purification of industrial gases as the hydrogen and argon, etc. Biological Action: Magnesium is an essential element for the animal and vegetable life. The photosynthetic activity of most of the plants is based on the absorption of the energy of solar light, to transform water and carbon dioxide in carbon hydrates and oxygen. This reaction is only possible due to chlorophyll presence, whose pigments have a rich composition in magnesium. In the animal systems, magnesium also plays an important role in enzymatic catalysis reactions involving the phosphate group, which are associated to the energy transfer and the stimulus at the muscular level. The lack of magnesium in the human body can induce diarrhea or vomits as well as hyperirritability or a slight tissue calcification. In extreme cases, this deficiency causes tremors, disorientation or even convulsions eventually leading to death. An adult daily diet must include 300 mg of magnesium for a good electrolytic balance. The body quickly eliminates the excess of magnesium. However, it should be pointed that magnesium compounds as the sulfate (Epsom salts) or the hydroxide, are laxatives and quite effective purgatives, so it should be used with moderation.
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13. Aluminum
History: Aluminum is the most abundant (8,13%) metallic element in the earths crust and after oxygen and silicon, the third most abundant of all elements in the crust. Because of its strong affinity to oxygen, it is not found in the elemental state but only in combined forms such as oxides or silicates. The metal derives its name from alumen, the Latin name for alum. In 1761 L. B. G de Morveau proposed the name alumine for the base in alum, and in 1787 Lavoisier definitely identified it as the oxide of a still undiscovered metal. In 1807 Sir Humphrey Davy proposed the name aluminum for this metal and later agreed to change it to aluminum. Shortly thereafter, the name aluminum was adopted to conform to the ium ending of most elements, and this spelling is now in general use throughout the world. Aluminum was also the accepted spelling in the United States until 1925 when the American Chemical Society officially reverted to aluminum. Hans Christian Oersted is now generally credited with having been the first to prepare metallic aluminum. He accomplished this in 1825 by heating anhydrous aluminum chloride with potassium amalgam and distilling off the mercury. Frederick Whler improved the process between 1827 and 1845 by substituting potassium for the amalgam and by developing a better method for dehydrating aluminum. In 1854 Henri Sainte-Claire Deville substituted sodium for the relatively expensive potassium and, by using sodium aluminum chloride instead of aluminum chloride, produced the first commercial quantities of aluminum in a pilot plant near Paris. Several plants using essentially this process were subsequently built in Great Britain, but none survived for long the advent in 1866 of the electrolytic process, which has dominated the industry ever since. The development of the electrolytic process dates back to Sir Humphrey Davy who in 1807 attempted unsuccessfully to electrolyze a mixture of alumina and potash. Later, in 1854 Robert Wilhelm Von Bunsen and Sainte-Claire Deville independently prepared aluminum by electrolysis of fused sodium aluminum chloride, but this process was not exploited for lack of an economic source of electricity. Grammes invention of the dynamo (in 1866) changed this and paved the way for the invention of the modern process. In 1866, Charles Martin Hall of Oberlin (Ohio) and Paul L. T. Hroult of France, both of them 22 years old at the time, discovered and patented almost simultaneously the process in which alumina is dissolved in molten cryolite and decomposed electrolytically. This reduction process, generally known as the Hall-Hroult process, has successfully withstood many attempts to supplant it; it remains the only method to produce aluminum in commercial quantities. Occurrence: Most of the aluminum produced today is made from bauxite. The only other ore serving as a raw material for aluminum is nepheline, a sodium potassium aluminum silicate. Bauxite derives its name from the village of Les Bauxs in Southern France where it was discovered in 1821. The term is generic. It refers to an ore or to a mixture of minerals rich in hydrated oxides, formed of aluminous rocks such as nepheline, feldspars, serpentine, clays, etc. During weathering the silicates are decomposed and the decomposition products (silica, lime, soda, potash, etc.) are leached out, leaving behind a residue enriched in alumina, iron oxide, and titanium oxide but still containing some silica. In tropical and subtropical regions the weathering process is more intense, and this is where most of the large bauxite deposits are found, at or near the surface. Most bauxite contains 40-60% alumina, either as the trihydrate gibbsite or as the monohydrates boehmite and diaspore. Boehmite prevails in bauxite found in a broad belt along the Northern Mediterranean. These deposits, extending from Spain through Southern France, Italy, ex-Yugoslavia, Austria, and Hungary to Greece, provide the base for the European aluminum industry. The biggest gibbsite deposits are found in tropical regions.
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Applications: The oxide quickly formed in surface of the pure metal turns it ideal for a lot of decoration applications. Because it has high electrical conductivity, ductility and low atomic mass, it is frequently used in electrical transmission lines. The metal has also been used in the coating of telescope mirrors, as well as in the production of aluminum leaves, used in the packing of victuals. In the pure form, the metal has a small mechanical resistance, being therefore generally used in alloys with copper, manganese, silicon, magnesium and zinc, with a wide range of mechanical properties. These alloys are used in construction, airplane and automobile structures, traffic signs, heat dissipatives, storage deposits, bridges and kitchen utensils. Hygienic Aspects: Aluminum is inert in the body. In spite of this, injuries to the pulmonary system and fibrosis have been found in animals exposed to prolonged inhalation of heavy concentrations of aluminum dust. In contrast to copper and a number of other metals, aluminum does not accelerate the loss of vitamins in cooking. The aluminum intake due to cooking in aluminum utensils is insignificant. The fact that the aluminum compounds have been used for years in the therapy of peptic ulcers and gastric hyperacidity without any apparent ill effects shows that the oral toxicity of aluminum is practically negligible.
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14. Silicon
History: Elemental silicon was prepared for the first time by Berzelius, in 1823, who placed silicon tetrafluoride in the presence of warm potassium. However, it was thought that GayLussac and Thenard had already tried to obtain the amorphous silicon by the same method, in 1809. The substance obtained by Berzelius was a purer product as a result of exhausting filtering. Berzelius prepared silicon from the reaction of potassium fluorsilicates with potassium. In its crystalline form, silicon was first prepared by Deville, in 1854, through the electrolysis of impure sodium-aluminum chloride with about 10% of silicon. At the beginning of the 20th century (1907), Potter studied the interaction of silica with the carbon, which prepared the way to the process of obtaining silicon for commercial purposes during the whole century. The elemental silicon is commercially prepared by the heating of silicon dioxide with coal in electrical furnaces. To obtain monocrystalline silicon one can use the method of Czochralski that consists of introducing a crystalline seed in melted silicon, slowly lowering the temperature so that it crystallizes. The common glass used to produce windows or bottles is primarily silica (75%), being the remaining 25% a mixture of Na2O (15%), CaO (8%) and Al2O3 (2,7%). Sometimes some "impurities" are introduced in the glass, such as boron compounds, to increase the resistance to heat giving the commonly known "Pyrex". Occurrence: Silicon occurs in Nature combined with oxygen, in the form of silicon dioxide, and with oxygen and several metals, in the silicate form, but is never found isolated. As a whole, the silicates and the silica represent 60% of the terrestrial crust. The SiO4 is the primary structural unit of all these substances. Actually, the silicates are a very extensive group of compounds, resulting from the combination of complex metallic ions or complex negative ions with SiO4 units. There are mineral silicates of almost all the 42 metals and non-metals besides the rareearths. The silicon dioxide, commonly called silica, is one of the most important silicon compounds occurring in Nature. This compound occurs in three different crystalline forms: quartz, tridymite and cristobalite. These last two can only be found in volcanic rocks and do not have industrial applications. During the test of the first atomic bomb in New Mexico other silicon crystalline form appeared: the keatite. The quartz is very common and it can be found in granite, sand and sandstone. It is a piezoelectric substance used to stabilize amplifier circuits, to measure high electrical potentials (thousands of Volts) or to measure high instantaneous pressures. There are sufficiently big and pure quartz crystals in the Nature to be used for optical purposes. There are also several forms of amorphous silica with water, such as the opal or the geyserite. From these, the black opal of Australia stands out, being one of the most valuable precious stones. Applications: The elemental silicon is used in silicone preparation, production of metallic alloys with iron, aluminum, copper and manganese or as deoxidizing agent in steel production. The iron-silicon alloy is produced by the simultaneous reduction of ferric oxide and silica with carbon, at high temperatures in an electrical furnace, with application as deoxidizing agent in the production of magnesium and chromium. The addition of a small amount of silicon to the aluminum alloys (about 14%) increases its consistency and its resistance to the corrosion caused by the seawater. Pure elementary silicon when doped with traces of elements such as boron and phosphorus is one of the best semiconductors. These substances have a myriad of applications in modern technology, because it was on the basis of semiconductors that transistors and diodes were invented. They are the core of any analog or digital electronic circuit. The semiconductors are also used in power rectifiers or in solar cells. Biological Action: Silica occurs in living organisms. It is possible that silicon may have played an important, perhaps even necessary role, in the origin of life on the earth. The pattern of deposition of silica in plants is biologically specific and it is possible to identify plants by
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microscopic examination of silica particles. In some cases, silica appears to be a factor in the resistance that plants offer to diseases and insects. Human tissues often contain from 6 to 90 mg of silica per 100 grams of dry tissues. Lung tissue may vary from 10 mg in infancy to as much as 2000 mg per 100 grams in old age. Miners, stonecutters, potters and others engaged in work where siliceous dust is breathed in large amounts often develop a serious lung disease called silicosis.
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15. Phosphorus
History: Phosphorus is the first element to be discovered having an historical register. In 1669, a German merchant called Henning Brand obtained elementary phosphorus through the distillation of urine, writing a letter to Leibniz reporting its discovery. It is quite probable that, in the 12th century, Arabian alchemists have obtained the element using this process. However, the credit is given to Brand. The name of phosphorus has a Greek origin meaning "it possesses brilliance" due to its property of shining in the darkness when exposed to the air. Further investigations by Brand's contemporary researchers revealed that the addition of sand or coal to urine helped the freeing of phosphorus. About one century after its original work, Brand discovered that phosphorus is an important constituent of the bones, introducing a new method of industrial production of phosphorus. The reaction of the bones with nitric or sulfuric acid produces phosphoric acid that, when heated up with coal, produces elementary phosphorus. This was the first method of phosphorus commercial production. At the end of the 19th century, James Readman developed the first process for the production of the element with an electrical furnace. In spite of many design and operation improvements of electrical furnaces, the basics of Readman's method to obtain elementary phosphorus remains in present technology. Occurrence: Due to its important role in biological processes, phosphorus is one of the most dispersed elements in Nature. It does not occur as a free element, but is common to find in the phosphate form in about 0,10% of earth's crust. It is the 11th more abundant element occurring in almost all volcanic and sedimentary rocks. Phosphorus occurs in almost all the volcanic rocks, having been present in the volcanic eruptions during the period of Earth formation. The erosion, by water, of the deposits of volcanic phosphates, and later assimilation by prehistoric plants, introduced the phosphorus in the biological mechanisms. The phosphorus can be found in almost 190 different minerals, but only the apatite series has an important role as phosphorus source. This series is represented by the following formula for a unitary cell Ca10(PO4)6 (F, Cl or OH)2. Phosphorus is present in the bony tissues and in the teeth as hydroxyapatite, but the greatest phosphate deposits in Nature are composed mainly by fluorapatite. The deposits of rich phosphate rocks are considered to be 50 thousand million tons. These occur primarily in the Northern Africa and the remaining distributed through the territories of USA and Russia. Applications: The elementary phosphorus is used in several pyrotechnic applications (fireworks, luminous projectiles or in commonly denominated matches), in the metallurgical industry to form metallic alloys as the phosphorous brass, in the production of insecticides or as addictive of industrial oils. The phosphoric acid is used as addictive for certain drinks as well as in the cleaning of some metals or as phosphatizing agent. But it is in the form of phosphate salts that the element has the largest applications. The fertilizer industry almost absorbs all extracted phosphates of the rocks. There are several types of fertilizers obtained from phosphates, usually mixed with potash or ammonia salts. The phosphate salts are also used in the production of synthetic detergents (sodium polyphosphate) and in teeth paste (calcium phosphate). Some condensed phosphates are used in industrial water treatment. Biological Action: Phosphorus is an element of vital importance in the growth and health of plants and animals. As hydroxyapatite, phosphorus is an important constituent of the teeth and of the bones. As triphosphate adenosin (ATP), or other organic phosphates, the element has an indispensable role in biochemical processes. All the biological mechanisms that use phosphorus use it as orthophosphate form or, alternatively, as polyphosphate, which by hydrolysis, becomes orthophosphate. Examples of these processes are photosynthesis, fermentation, metabolism, etc. In the living animals, phosphorus is also a constituent element of the nervous tissues as well as of the cellular plasma.
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16. Sulfur
History: Occurs in Nature in free and combined states, being already known in the Antiquity by its color, combustion easiness and scent. Homer mentions the use of its combustion products as disinfectant, and Dioscoride also describes its application in Medicine. It was well known to the alchemists, just as sulfuric acid, compound of this element. In 1772 Lavoisier proved that the sulfur is an elementary substance. Occurrence: Sulfur occurs mainly in the sulfate form, as, for example, the calcium sulfate (anhydrite), magnesium sulfate (Epsom salt and kyeserite), barium sulfate (barite), strontium sulfate (celestite), and sodium sulfate (glauberite). All the spring waters have the sulfate ion and some have also hydrogenate-sulfide (sulfuric waters). This element can also be found, in the form of metallic sulfides, in pyrite, calcopyrite, galena, blende, rosalgar and the cinnabar. Volcanic gases contain sulfur dioxide and hydrogen sulfide, which can also be found dissolved in the sulfuric waters. The most important sources of sulfur are the mines of sulfur in the native state that can be found mainly in the USA (Louisiana and Texas), and in Japan. In Europe, the main deposits are in Sicily. In Spain, there are deposits in the Mountain of Gador (Almeria). In Portugal, it occurs in the Furnas of S. Miguel (Azores). Applications: Among the typical sulfur reactions, the reaction with the olefins, of great technological importance should be pointed out because it is the base of the so-called process of vulcanization of natural and synthetic rubber. The most important sulfur compounds, from the industrial point of view, are: sulfur dioxide, gas obtained by combustion of the sulfur to the air, with a suffocating smell, used in the production of sulfuric acid and in bleaching; hydrogen sulfide, also called sulphydric gas, extremely poisonous and with characteristic smell to rotten eggs, considered a weak acid in aqueous solution and tending to form colored compounds not very soluble with most of the metals (used for this reason in chemical analysis); sulfuric acid, an oleaginous liquid widely used in laboratory and in several industries; and the carbon sulfide, liquid applied as solvent. The sulfur is mainly used in the production of several compounds as the sulfurous gas, sulfite, sulfuric and sulphydric acids, carbon sulfides and others. It is also used in the production of the black gunpowder and of insecticides, pharmaceutical products and disinfectants, as well as in the vulcanization of the rubber for the process already referred. The sulfurous products are used as addictive in scentless combustible gases, so that the escapes can be detected through the characteristic smell of the element. It should be finally pointed out, that S 35 is applied in biochemistry for elucidation of reaction mechanisms. Biological Action: Sulfur is an indispensable element of life. Plants manufacture its own aminoacids, which contain sulfur (cistin and metionin), by reduction of dissolved sulfates. The element is also a minority constituent of fats, corporal liquids and of the skeleton, being almost as abundant, in the organisms, as phosphorus. In the human body the sulfur can be found of sulfates bound with organic compounds. The hydrogen sulfide, when in small concentrations, can be absorbed; however, in larger doses it causes death by breathing paralysis. The carbon disulfide can also be lethal but has a narcotic effect when ingested in reduced doses. The compounds of sulfur are not cumulative poisons. In spite of these effects, elementary sulfur is physiologically inert.
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17. Chlorine
History: Chlorine was discovered in 1774 by K.W. Scheele, a Swedish chemist; he liberated this element for the first time by heating manganese dioxide with hydrogen chloride, HCl, an acid first made by alchemists in the 15th century and named "muriatic acid" by the French chemist Lavoisier. Scheele thought that the yellow-green product gas was a compound, naming it "oximuriatic acid" because he thought that the gas resulted from the combination of oxygen and "muriatic acid". This erroneous opinion was supported by the work of Berthollet, in 1785, who observed the production of oxygen when the chlorine solution was exposed to light. Gay-Lussac and Thnard, in 1809, tried to separate its components by exposing the pure dry gas to incandescent carbon. Davy, in 1810, tried again to do this separation, but was obviously unsuccessful, concluding that it was an element, not a compound. Davy named this new element as chlorine, derived from the Greek chloros that means greenish-yellow. Occurrence: Chlorine abundance in the lithosphere is estimated to be about 0.045% by weight. Due to its strong chemical affinity for the other elements, it never occurs in the free state, except as a minor constituent of the gaseous output from volcanic eruptions. Rock salt or halite (NaCl) , sylvite (KCl) and carnallite (MgCl2.KCl.6H2O) are among the most common minerals consisting of chlorides. Beside being dispersed in the lithosphere, chlorine salts are also dissolved in the hydrosphere. In the hydrosphere as well as in the lithosphere sodium chloride, NaCl, is by far the most common of alkali metals: hence its name of "common salt". The average concentration in seawater is approximately 2,6%. Due to its unreplaceable function in human diet it is also known as "table salt" and the uneven distribution of its deposits over the earth's crust has played an essential role in conditioning the pattern of civilization in time and space. The occasional use of this commodity as a valuable currency is still reminded by the word "salary". Applications: Chlorine has a lot of applications. It is used with hygienic purposes and is indispensable in water treatment, being also used for disinfecting of industrial residues and pool cleaning. Due to its decolorizing properties it is used in the whitening of vegetal fibers like cotton, linen etc., and of paper pulp. It is also used in industrial production of organic compound, like carbon tetrachloride, chlorobenzene, synthetic glycerin, etc. Biological Action: Chlorine gas has a characteristic pungent odor with a detectability threshold of a few parts per million in air. Liquid chlorine in contact with eyes, skin, or clothing may cause severe burns; as soon as it is released in the atmosphere, it vaporizes with irritating effects and a suffocating action, which were exploited in World War I by using it as a war gas. Although it is only detectable by smell at 3,5 ppm, it causes severe irritation of the throat at 15 ppm. It is extremely dangerous to bread in a 40 ppm atmosphere. A dosage of 1000 ppm is lethal. Due to these effects, chlorine is considered a dangerous substance so special care should be taken in its manipulation.
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18. Argon
History: Argon was the first of the inert gases to be discovered on Earth. Its discovery illustrates curious omissions that sometimes occur in science. In 1785 Cavendish mixed air with oxygen and performed several electrical discharges over a mixture of potassium hydroxide. By this process, he converted nitrogen of the air into potassium nitrate. Then, he removed the oxygen excess, but still remained a small amount of gas, not larger than 1/120 of the original volume of air. He considered that this difference had been caused by experimental errors. Almost 100 years after, in 1894, Lord Rayleigh made a series of measurements of the density of nitrogen from several sources. He verified that the density of the nitrogen of the air (1,2572) was always larger than the density of the nitrogen present in compounds (1,2506). This difference was too big to be imputed to experimental errors, leading him to conclude that the atmosphere had to contain an heavier inert substance. Lord Rayleigh, working with Ramsay, repeated the experience of Cavendish, removing the nitrogen with heated magnesium. The residue revealed an unknown spectrum, and it was shown that this new gas was not combined with the nitrogen. Argon was called (from the Greek word for "inactive"). Occurrence: Argon can be found in Nature, constituting 0,941% in volume in the air (with no carbon dioxide). Its proportion in the air is approximately constant, however, above the sea is slightly higher. The argon is more soluble in water than nitrogen. Therefore, its proportion in liquid air is larger than in the atmosphere. The argon was also discovered in natural gas and in some minerals. It always appears associated with nitrogen. Applications: Argon is mainly used in welding and in other operations that demand a nonoxidizing atmosphere without nitrogen. Since 1920 it is used in the filling of electrical lamps, in order to reduce the evaporation speed of the tungsten filament and, more recently, in thermalionic tubes "thyratons" and in fluorescent lamps.
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19. Potassium
History: Metallic potassium was first obtained by Sir Humphrey Davy, in 1807, by electrolysis of potassium hydroxide. He called it potassium from the English term "potash" ("pot" - recipient + "ash" - ashes), the name given to potassium carbonate obtained by lixiviation and evaporation in iron recipients of the wood and plant ashes. Ever since, the potassium has been progressively replaced by sodium, in most of the salts with industrial applications, with exception of the cases where the specific properties of potassium salts are required, as it is the case of the fertilizer industry. Occurrence: The element is widely distributed in Nature, being the seventh in abundance order. The ocean water contains about 0,07% of potassium chloride, and it is necessary to evaporate 98% of this to make potassium salts start to crystallize. Potassium can be found in many volcanic rocks, which by disintegration supply the element to the soils and the water. The silicate leucite and glauconite are the commercial sources of potassium. The clays can absorb potassium retaining it in the soil and allowing the plants to use it. The main potassium ores are: the sylvite (KCl), the carnalite (KCl.MgCl2.6H2O), the langbeinite (K2SO4.2MgSO4), and the polyhalite (K2SO4.MgSO4.2CaSO4.2H2O) that can be found in Germany, USA, Canada, Russia, Palestine, Congo, Ethiopia, Brazil and Bolivia. Applications: Potassium forms alloys with many metals, but only the alloy obtained with the sodium has some interest in the technology of nuclear reactors. The more important compounds, from the point of view of applications, are chloride, sulfate, nitrate, carbonate and hydroxide. The salts are used not only as constituents of fertilizers but also for other more specific goals. The sulfate is used as addictive of the gypsum to control its hardening speed and its resistance, the carbonate is used in the production of special glasses and in ceramics, and the nitrate is used in the production of explosives. The chloride, as well as the hydroxide, are the main sources to obtain other salts; the latter one is also used as industrial reagent for producing liquid soaps, as electrolyte in certain batteries and as absorbent of carbon dioxide and hydrogen sulfide. Other less common salts are used in Medicine: the bromide as sedative, the permanganate as bactericide, etc. Biological Action: Potassium is an indispensable constituent for the correct development of plants, it is therefore present in almost all type of soils, in several forms and with different solubility degrees. The potassium ion is absorbed by the soil through the humus compounds, or through clays or natural zeolites. The deficiency of the element in the soil implies plant atrophy, mainly of the roots. Potassium can also be found in the animals' cellular liquids in the form of monopositive ion and has an extremely important role in several biological reactions and vital manifestations, such as transmission of nervous pulses to produce muscular contraction. Disturbances in the amount of potassium and sodium, and its compounds, in the living organisms have usually disastrous effects at the metabolic level.
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20. Calcium
History: The knowledge of calcium as a chemical element is relatively recent. However, some of its compounds are known and used since early times. The Romans used lime (calcium oxide), clacked lime (calcium hydroxide) and hydraulic cement in construction works. The name of the element is derived from the Latin calx (lime). The element was first isolated by Sir Humphrey Davy, in 1808, by electrolysis of the fused chlorides. In a reunion at the English Royal Society, in the 30th July 1808, he referred to the new alkaline earth metals in this way: "These new substance require new names and therefore by the principles used in the naming of the alkalis, I suggest the names barium, strontium and calcium". Occurrence: Calcium is a very reactive and does not occur as a free element in Nature. It is present in the earth's crust in the forms of carbonate, sulfate, fluoride, silicate and borate. The calcium carbonate occurs in marble, chalk, limestone and calcite. Calcium sulfate (CaSO4) occurs in anhydrite and gypsum, calcium fluoride in fluorspar or fluorite (CaF2) and calcium phosphate occurs in apatite. Calcium also occurs in numerous silicates and aluminosilicates. Almost all natural waters, including seawater, contain either or both calcium carbonate and calcium sulfate. Many organisms concentrate calcium compounds in their shells or skeletons. For example calcium carbonate is formed in the shells of oysters and in the skeletons of coral. Applications: Calcium has significant applications in the production of alloys with lead and aluminum, and in the industrial production of metals from its oxides. It is also used as deoxidizer with iron, steel, copper and its alloys. Calcium carbonate is the most important of all calcium compounds. It appears in colorless crystals, like calcite, which has birefractivity properties, or in other crystalline form, as aragonite. It is the major constituent of pearls and sea shells, being present in calcareous formations of caves. For use in the chemical industry most calcium carbonate is first converted to lime by an heating process. This lime can origin cement if mixed with water and sand. The heating of calcium oxide in an electrical oven with oven-coke produces calcium carbonate also called "carbite". This can react with water to origin acetylene, one of the most important compounds in organic chemistry. Calcium sulfide occurs in nature as the mineral anhydrite, crystallized in rhombic prisms. Calcium metaphosphate is used as a mild abrasive and as neutralizing agent in toothpastes. The monobasic phosphate is used as fertilizer, and calcium chloride when mixed with ice is an excellent freezing and exsiccation agent. Calcium fluoride, constituent of fluorite, is used as a flux, but, more important, is the source of hydrofluoric acid made by the action of sulfuric acid on fluorspar. Calcium "hipocloride" is used as decolorizer, oxidizer or disinfectant. Biological Action: Calcium is an essential element in living organisms. It plays an important role in the metabolism of nitrogen in some plants where a deficiency of calcium leads to poor absorption of nitrogen. Lack of calcium in plant nutrition leads to a reduction in the number and size of the chloroplasts. Calcium is the most abundant inorganic element in the higher animals and is located principally in the bones and teeth as apatite, a calcium phosphate mineral. Blood is also a huge reservoir of calcium in animals. Calcium is distributed throughout all tissues where it has special roles in controlling nerve impulse transmission, muscle action, blood clotting and cell permeability. Calcium deficiency is exhibited by the onset of rickets, failure of the blood-clotting mechanism, nervous disorder and convulsive muscular contractions. Vitamin D greatly improves the absorbability of calcium ion and the value of this vitamin in treating rickets is based in part on this effect. Large intakes of calcium lead to excessive calcification and kidney stones.
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21. Scandium
History: Scandium was discovered in 1876 by Lars Fredrik Nilson, in Uppsala, Sweden, through the study of the euxenite ore, although its existence had already been inferred by Dimitri Mendeleev in 1868, based in its Periodic Table of the Elements. It is not a rare element, being twice more abundant than boron. However, it is extremely difficult to obtain in a pure state, so its chemistry is not very well known. After its discovery, scandium was treated just as like a rare-earth, due to its common characteristics. However, the discovery of new physical and chemical properties, claimed different treatment for this element. Metallic scandium was first prepared in 1937, by Fischer and collaborators, through the electrolysis of scandium chloride in a mixture of several melted salts. However, the obtained product still contained about 5% of sludge, mainly iron and silicon. Occurrence: Scandium can be found in the terrestrial crust in a concentration of about 5 ppm being as abundant as beryl, or some rare-earths. In spite of this, it is quite dispersed, occurring in small concentrations in minerals as wolframite, wiikite and cassitherite, and can be detected in most of the soils. Scandium is chemically similar to the rare-earths but the sizes of its ions compete with those of aluminum, magnesium, hafnium and zirconium, so there are no great amounts of the element in the rare-earths ores. In 1911, Schetelig, in Norway, discovered a new mineral, that he called tortveitite, contained the amazing amount of 30 to 40% of ScO2. This mineral was also found later, in Madagascar. The tortveitite occurs in very small amounts in the form of prismatic residual crystals resultant of pegmatite veins erosion as those of the Norwegian black uraninite. It is also possible to obtain scandium through the processing of uranium ores, which contain small concentrations of the element. Applications: The relative likeness between scandium and yttrium seems to extend to the respective metallic alloys. Thus, metallic alloys of rare-earths are similar to scandium ones, whose applications are limited to the metallurgical industry. In a general way, scandium does not tend to form alloys with alkaline metals. However, this element is sufficiently soluble in magnesium for hardening it. There is also evidence that the scandium can be dissolved in titanium at high temperatures. Biological Action: Just as yttrium or the rare-earths, scandium is dangerous to human health, due to its toxicity. It must, therefore, be treated and manipulated with extreme care.
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22. Titanium
History: Titanium was discovered in 1791 by William Gregor during his study of magnetic sand (menachanite) from Menachan in Cornwall. He called it "menachin". Three years later, M. H. Klaproth discovered what he thought to be a new earth in the rutil. He called it "titanium" (from the Latin titans, which means "children of the Earth") and showed that it was identical to the "menachin" obtained by Gregor. The metal was first isolated by J. J. Berzelius in 1825. Hunter prepared pure titanium, in 1910, by heating up titanium and sodium tetrachloride. Occurrence: Titanium does not occur free in Nature. However, when combined with other elements, it is quite abundant, occurring in small amounts in most of the volcanic, sedimentary and metamorphic rocks. Its more important minerals are the ilmenite, the rutile, the arizonite (iron titanate), the brookite, the anatase, the leucochene (titanium dioxide), the perovskite (calcium titanate), and others. The first two have commercial importance, and can be found in deposits spread all over the world. There are important rutile and ilmenite deposits in Australia, Argentina, USA, Central Africa, Brazil, Canada, Egypt, India and Norway. The largest well-known deposits of rutile are located in Australia. Applications: The more important compound, from the industrial point of view, is the dioxide that, because of its extreme whiteness and high reflectance, is widely used as pigment in the production of inks, lacquers, enamels, paper, rubber, textile, plastics, ceramic and cosmetics. When crystallized, rutile is also used in the production of artificial precious stones that imitate diamond. Among the remaining compounds the titanium (IV) sulfate, used in the production of the dioxide, and the titanium (III) sulfate (with a blue color), which is a powerful oxydizer, deserve special reference. The titanium (IV) halogens are used in the production of the so-called smoke curtains; the salts of organic acids are used as mordant for coloring and also in tannery. The titanates, especially the iron one, are important raw materials for obtaining the metal; the barium titanate possesses piezoelectric properties. The metal is widely used in the production of equipment that demands lightness combined with mechanical resistance. It is mainly used in the military and aeronautical industries (helixes, turbines, reactors, missiles, etc.). In most of the cases it is used in the form of alloys with other metals as the aluminum, iron, manganese, chromium, molybdenum and vanadium. These applications take over 90% of the total production of titanium; the remaining is destined to the manufacture of equipment for the chemical industry. Biological Action: Titanium dioxide is a non-toxicant compound. However, several other compounds of titanium have considerable degrees of toxicity, with special relevance to the organic compounds. Titanium compounds act as catalysts in oxidation reactions in the vegetable cells, being also known that the element is essential to the formation of the soils. Titanium tetrachloride is strongly irritant to the skin and, when inhaled, is extremely dangerous.
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23. Vanadium
History: In 1801, Manuel Del Rio found, in a Mexican ore, what he thought to be a new metal. He called it "erythronium" (from the Greek "erythros" that means "red"), since the metal produced red salts when treated with acids. However, Del Rio abandoned its opinion when, four years later, Collet-Descostils affirmed that the new metal was just an impure chromium oxide. In 1830, N. G. Sefdtrm described a new mineral that had been found in Swedish ores containing iron, and called it "vanadium", in honor of "Vanadis", a Swedish goddess, due to the brilliant colors of its compounds. In 1831, F. Wller discovered that Del Rio's erythronium was not anything but the vanadium of Sefdtrm. J. J. Berzelius also investigated this vanadium in 1831, but he thought that vanadium oxide was a metal, itself. Finally, in 1867, H. E. Roscoe isolated the metal and established its relationship with the nitrogen family. Occurrence: Vanadium is widely distributed in Nature, and can be found in charcoal and in crude oil. It can also be found in some ores, like pathronite, a vanadium sulfide, that can be extracted in the Mina Ragra in Peru. As these deposits are being consumed and the vanadium needs increases, the metal began to be extracted from another minerals, such as carnotite (Colorado, Arizona, New Mexico) and some titan-ferrous magnetite. Other vanadium minerals, although of smaller importance, are the bravoite (Mina Ragra, Peru), the sulvanite (Australia), the roscoelite (Colorado and Utah, EUA), the davidite (Australia), the uvanite (Utah, USA) and the vanadinite (Mexico and Argentina). Applications: Its more important compounds are the pentoxide, raw-material used in the production of most of the other ones, and the ammonia metavanadate, which is used as catalyst in the chemical industry, for producing sulfuric acid. It can also form alloys, in particular with the iron, to improve its mechanical properties and strength. The alloy made with aluminum is useful in prepararing of several others, such as titanium, vanadium and aluminum, used in the aeronautical industry. Biological Action: Vanadium does not have any defined biological functions in the animals, but can be found in a breathing pigment in the blood (blue) of a kind of marine worms (gen. Ascidia). Vanadium can also replace phosphorus in the apatite molecule (P2O5) which is an important constituent of the teeth. Vanadium and its compounds should be viewed as toxic materials. They must be handled with special care.
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24. Chromium
History: In 1782, J- G. Legmann, in a letter written to the naturalist G. L. L. de Buffon, described a new Siberian mineral, known today as crocoite (lead chromate). Neither Vaquelin nor Macquart, in 1789, were able to find any new element in this ore. This test only revealed lead, iron, alumina and a great amount of oxygen. However, in 1797, Vauquelin re-examined the mineral and concluded that the lead should be merged with some other compound which he thought to be an oxide of a new metal. He called chromium (from the Greek "chromos", that means color), because its compounds were very colorful. One year later, he was able to isolate the metal by the heating of chromium oxide (Cr2O3) and charcoal. In 1893, Moissan reduced the chromium oxide with charcoal in an electrical furnace and in 1898, Goldschmidt prepared chromium without traces of carbon by reduction of Cr2O3 with aluminum. Occurrence: Chromium is never found free in Nature and most ores consist of the mineral chromite. The ideal formula for this ore is FeO-Cr2O3, containing 68% Cr2O3 and 32% FeO, but the actual composition of the higher grade ores varies, with also varying amounts of magnesia, alumina and silica. The main sources of chromite are the former USSR, South Africa, Philipines and Zimbabwe. Applications: The chromates and the dichromates have a lot of applications. They are used in tanning, as mordants, in dye production, as wood preservers, in the production of pigments used against metal corrosion (electroplating), etc. In the electroplating process, the metallic pieces take a bath in a CrO3 solution. An electrical current is then passed through the metallic pieces (cathode) and the anode, also immersed in the solution and usually made of a lead-antimony alloy. The plating takes place in a fine coating around the metallic pieces. Biological Action: Pure metallic chromium, chromite and trivalent compounds do not produce any serious damage to body tissue. The toxic action of chromium is confined to the hexavalent compounds, which exert an irritative, corrosive and possibly toxic action on the human body. Under certain conditions these compounds cause denaturation and precipitation of tissue proteins. Intimate contact, as in industrial exposure, affect primarily the skin and the respiratory tract such as ulcers and dermatitis. There is increasing evidence that the incidence of cancer of the respiratory tract is abnormally high among workers exposed to hexavalent chromium dusts during chromium refining.
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25. Manganese
History: The manganese compounds were already used in the Antiquity, but it is difficult to determine the beginning of its usage, once they were mistaken by other compounds such as those of iron and of another elements. Pliny, in the Roman Era, mentions its usage with the name of "magnes", considering it a magnetite variety, i.e. a magnetic mineral of iron. Later, in books of the end of the 17th century, the term "magnesia" was used as synonym of manganese oxide. J. H. Pott in 1740, proved that pyrolusite (manganese dioxide) does not contain iron, as it was believed until then, produced a wide variety of salts, which were different from those obtained from the iron oxides. In 1774, C. W. Scheele distinguished the magnetite of the pyrolusite, and, in the same year, his assistant Johann Gottlieb Gahn isolated the manganese. Its name derives from the Latin magnes, which refers to the magnetic properties exhibited by the pyrolusite. Occurrence: Manganese is widely distributed in the terrestrial crust. It is usually associated with the iron ores, in relatively small concentrations. The principal manganese ores are pyrolusite (MnO2), psilomelane, manganite (MnO(OH)), braunite (3Mn2O3.MnSiO3) and hausmannite (Mn3O4), that can be found in Brazil, Gabon, India, Ghana, Congo and South Africa. Other manganese ores, although less important, are rhodochrosite (MnCO3) and rhodonite (MnSiO3). Applications: The major application of the pure manganese is for making iron-manganese alloys. This absorbs more than 90% of the its total production. It is also used in non-ferrous alloys with aluminum and magnesium, copper, nickel and zinc. In the production of steel, the presence of the manganese is essential for sulfur control, and, in special steels, for the control of carbon and phosphorus. There is a wide range of compounds of this metal, but only a scarce dozen is manufactured and has industrial interest. The principal is the dioxide, used in the production of the metal and in production of Le-Clanch batteries and as oxidizer agent used, for example, in the preparation of the hydroquinone from the aniline. The manganese oxide is used as a manganese source in fertilizers and it constitutes the usual intermediary product in preparing compounds of this element. The manganese sulfate is used for producing the metal by electrolytic processes, in manufacturing inks and varnish, in dyeing, in ceramics and as manganese source in fertilizers. The potassium permanganate is a purple colored compound, with strongly oxidizing properties, being used as disinfectant. Due to its properties, still finds usage in water treatment, in air purification and in the preparation of certain organic compounds, as for example, the saccharine. It is also widely used as analytic reagent. Finally, we refer to the salts of organic acids, as naftenate, oleate and linoleate, used in oils for inks and varnish. Biological Action: It is an essential element of the animal and vegetable life. It appears in some enzymes and, probably, it conditionates the use of some vitamins (B1). For these reasons it is frequently added to fertilizers and to pharmaceutical preparations (glycerphosphate and manganese hypophosphide). Its deficiency causes the chlorophyll decrease in the plants (that acquire a yellowish aspect) and disturbances in the bone tissues of the animals. Generally, the manganese compounds are not toxicant. However, the oxidizer properties of some permanganate can cause skin irritation and the inhalation of its vapors can be quite harmful.
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26. Iron
History: Iron is probably the most precious of all metals, since man would certainly miss this element more than any other, even the so-called precious ones. In the beginning of the 14th century, when iron was rare, some iron kitchen utensils of Edward III where classified as jewelry, and iron accessories were preferentially seek by robbers. The name "iron" comes from the Scandinavian "iarn". Many fantastic stories have been told about the origin of iron. Some of them say that was iron a gift of the Gods while others try to describe it as coming from meteoric sources. However, we do not need this kind of explanation if we consider that iron can be reduced from several ores present in Nature. It is told that iron was produced for the first time when some pieces of ore, used in cook fires, reduced, when fires were kept long enough. After this, it was observed that higher temperatures (and wind) lead a better iron. This method was improved by several tricks until the creation of the furnace. Iron has been known and used since prehistoric times. The writings of the most early civilizations refer to it, and there is evidence that it was known more than 7000 years ago; in China the usage of steel goes back to 2550 a.C.. Some vedic poets wrote that their prehistoric ancestors already knew iron and were able to transform it into utensils through a considerable range of technics. Considering that iron utensils are less frequent than those of bronze, archaeologists consider the Bronze Age before the Iron Age. In fact bronze is easier to extract and work than iron. They believe that bronze was abandoned as utensil and weapon by 500 a.C.. The lack of copper and the abundance of iron lead the Hindus to develop new technics for iron working, later used in Europe by several civilizations such as the Etruscans in Northern Italy. After the fall of the Roman Empire, iron production suffered a considerable development in particular in Spain, being famous the steel blades of Toledo and its craftsmen. These craftsmen went to France and Germany, where they introduced the bloomery which developed and originated the big furnaces. The by-products of the bloomery were a kind of malleable iron or steel; the big furnaces produced a wide variety of iron that could not be hardened but was suitable for other kinds of casting and moulding. The discovery, by Cort, of a transformation process of this kind from iron to forge-iron, with considerable lower production costs than the bloomery process, considerably increased the production in England. Occurrence: The principal iron minerals are hematite (Fe2O3), magnetite (Fe3O4), limonite (Fe2O3.H2O) and siderite (FeCO3). The most common natural iron compounds are pyrite (FeS2) and ilmenite (FeO.TiO2) but are not suitable for the element extraction. The major deposits of iron are in the USA, France, Germany, Great Britain, Austria, Sweden and Russia. Other important producers are Brazil, Chile, Cuba, Venezuela and Canada. This element occurs in almost all the rocks (though in small amounts) and in living animals and plants. It is also easy to find in natural water springs. Applications: Iron is one the most useful metals. Its applications, as well as those of its alloys, are very important and well known, so are those of its compounds. The iron sulfate is used as fungicide, the oxalate of iron in photographic development, limonite and hematite as pigments and abrasives. Magnetite is used in the production of industrial electrodes, iron chloride and nitrate are used as mordents and industrial reagents mainly in the dye industry; "Prussian blue" and "turnbull blue" are used in the production of several types of inks. Iron carbonyl is used as catalyser of many reactions. Biological Action: Iron plays an important part in the metabolic processes of the animals, being a vital representative in the cells of all mammals. The function of the iron in the body is limited almost exclusively to the oxygen transport in the blood, through the hemoglobin. It is also present in some enzymes that catalyze reactions of cellular oxidation. In the human body, the
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richest organs in iron are the liver and the spleen. Although in smaller amount, it is also present in the bones, in the medulla, in the kidneys and in the intestines. An adult man absorbs about 5 mg of iron a day, while the woman absorbs slightly more to compensate the losses during menstruation or pregnancy. The absorption of iron is larger in children, exceeding 10 to 15 mg a day. There are several ferrous salts, as the ferrous sulfate, that are quite effective in the anemia treatment due to the deficiency of iron. Of the richest victuals in iron stands out the liver, the fish and the egg yolk. The beans and the peas and, in a general way, all the green vegetables are richer in this element.
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27. Cobalt
History: The word "kobalt" appears in the writings of B. Valentine and Paracelsus as a description of an elf imagined by the Teutins and the Ancient Scandinavian. These "elfs" used to haunt the mines, destroying the work of the miners. The word derived from the German "kobald", which means evil spirit. In some mining regions there were specific prayers to protect the miners from those "kobalds" and other evil spirits. This term was also used to the so-called "false ores", i.e, the ores incapable of giving any useful metal when submitted to extraction processes. Gradually this term was confined to the minerals used in the production of blue glass and smalts. In 1735, Brandt pointed out that the primary cause to the blue color of those glass and smalts was due to the presence of a metal or semi-metal, that he called "cobalt rex". Brandt was the first to isolate this metal in 1742. Occurrence: Cobalt is not an abundant elements but is widely diffused in rocks, sea and mineral waters, coal, meteorites, the sun and stellar atmospheres, soils, plants and animals. Relatively little cobalt ore is mined for the cobalt content, and most of the metal is recovered as a byproduct of ores treated for their copper or nickel content. The most common minerals containing chromium are carrollite, smaltite, cobaltite, asbolite, heterogenite and erythrite. These minerals are found and extracted in the Zimbabwe, Germany, Canada, Morocco and Australia. Applications: Cobalt and its compounds have several applications. They are used both in laboratory and industrial environment and catalysts; e.g., cobalt molybdena is a catalyst largely used in the oil industry in the oil reforming process. The well known 60Co is the most used radioactive isotope of this element. It is nowadays the most common source of radiation. It is used in the cold sterilization of food in the USA, Australia, England, France and Russia. Beside these applications, cobalt compounds are used in ceramics, glaziery, smalt and enamels, in the production and several alloys, special steels, in agriculture salts production and in cobalt plating. The compound used in the production of smalts is the Co3O4, used for example in enameling over iron and steel. In ceramics and paintings, these compounds are particularly useful for preparing pigments. The cobalt compound are also used in the preparation of "invisible ink" made of a roseous solution of cobalt chloride, which turns into a blue visible ink when heated. This compound is also used in some hygrometers. It turns to blue and pink by action of the atmospheric humidity. Biological Action: Cobalt is one of the oligo-elements indispensable to the correct development and growing of most of the animals. In particular, it is part of the B12 vitamin, or cobalamine, which is antianemic.
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28. Nickel
History: Nickel was first isolated by Cronstedt, in 1751, and first prepared as a pure metal, in 1804, by Richter, that also made a detailed description of its properties. In 1870, Fleitmann discovered that the addition of a small amount of magnesium would render nickel malleable. The element percentage in the terrestrial crust does not exceed 0.01%, being the 24th more abundant element in the Earth. However, there are few natural deposits of nickel that would justify its exploration. Occurrence: Nickel does not occur as native metal. Its main minerals are the sulfides, the silicates and the arsenides. In the sulfides we stand out the pentlandite, the millerite, the polydymite and the siegenite, that can be found in Canada, ex-USSR, Cuba and U.S.A. The silicates garnierite and nickeliferrous limonite can be mainly found in Canada (Sudbury), exUSSR, South Africa, Finland and USA (Minnesota). Among the arsenides we point out the niccolite, the gersdorffite, the chloanthite and the annabergite. Applications: Nickel has a lot of compounds and complex which present the oxidation states -1, 0, +1, +2, +3, +4. The compounds of Ni (0) are quite usual, with special relevance to the carbonyl Ni(CO)4, and they are a very volatile colorless liquid their used used in material plating. The oxidation state +2 is the most common one, being known a great number of compounds, namely the hydroxide Ni(OH)2, the oxide NiO, salts of all the inorganic acids and of a great number of organic acids. Among these we refer the sulfate, usually used in electroplating solutions, the acetate, used as catalyst and mordant in the textile industry, the formate, used in the production of catalysts, the isodecylorthophosphate and the naphthenate, used as motor oil and lubricants additives, and many other, with several applications in the laboratory and in chemical industry. Among the numerous nickel complexes (II), we refer to the di-n-butyldithiocarbamate, oxidation inhibitor in the industry of synthetic rubber, the dimethylglyoxime, used in analysis and as pigment in beauty products, the nickel phthalocyanine nickel (II), blue pigment used in the industry of the colorings, the nickelocene, organometallic compound used as catalyst, etc. Most of the world production of nickel is used for producing alloys: inox steels for the metallurgical and mechanic industry, special steels for the aeronautical industry, cupro-nickel for the manufacture of coins, chromium-nickel for cutlery, iron-nickel for magnets, coppernickel-zinc (German silver) for ornamental and domestic objects, etc. Another important fraction of this production is used in the plating of metallic pieces (electroplating) with ornamental purposes as a protection against corrosion. Among the remaining applications we refer the production of catalysts, especially the so-called Raney nickel, and compounds for multiple purposes. Biological Action: Due to its proximity to iron and cobalt in the Periodic Table, nickel properties are quite similar to those of the latter. Nickel and its compounds do not seem to be toxic. It was supposed that the ingestion of food prepared in kitchen utensils made of nickel alloys was dangerous. However, careful researches revealed that such is not true.
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29. Copper
History: The discovery of copper go back to prehistoric times; it has been mined for more than 6000 years. Gold was probably the first metal to attract man's attention because of its sparkling yellow color, and iron in the form of meteorites may have been used before copper in some localities. However, there is evidence that every ancient metal culture was actually introduced by the use of the red metal. The early age of copper probably had its greatest development in Egypt. The most important copper-ore deposits of Antiquity were in Sinai, Syria, Afghanistan, Cyprus, Iberia and Central Europe. European copper mines of the Bronze Age are known in Austria, Germany, France, Spain, Portugal, Greece and Tyrol. The world today's copper industry is confronted with many technical and economic problems; one of the most challenging is preventing the loss of markets to substitute materials such as aluminum, steel and plastics. Occurrence: Copper is widely distributed in many parts of the world - mainly as mineral combinations with iron, sulfur, carbon and oxygen. More than 160 copper minerals have been identified, but only about a dozen are commercially important. Copper minerals are conveniently divided into three groups. Primary or hypogene minerals, which are deposits at considerable depth in the earth by processes related to igneous activity, are represented by compounds such as bornite (Cu5FeS4), chalcopyrite (CuFeS2), enargite (Cu3As5S4) and similar combinations. The second group is composed of oxidized copper minerals, which are commonly formed by the weathering of copper sulfides exposed to erosion. Cuprite (Cu2O), malachite (CuCO3.Cu(OH)2), azurite (2CuCO3.Cu(OH)2) and chrysocolla (CuSiO3.2H2O) are the principal representatives of this group. The third group is that of the secondary sulfides which generally have been formed by copper leached from sulfides exposed near the earth's surface. Chalcocite (Cu2S) and covellite (CuS) are members of this group. The commercially more important minerals are chalcocite (with 79,8% of copper) and chalcopyrite (with 34,5% of copper). Minerals like enargite and other sulfides are usually extracted in open pits. The deep mining is less common, in copper extraction, due to its high costs. Applications: There are several cuprous (Cu+) and cupric (Cu++) compounds with many applications. The cuprous chloride is used extensively as a catalyst, desulfurizing agent and decolorizing agent in oil industry. Cupric chloride is used as a mordant in the dyeing and printing of textiles, as an oxidizing agent for aniline dyestuffs and in laundry marking inks. It's also used as a fungicide. The cuprous oxide is used in antifouling paints for steels and wood exposed to seawater and as a fungicide. Cupric nitrate is used in light-sensitive reproductive papers and the cupric fluoride has found use as an opacifier in enamels, glasses and ceramics. Copper sulfate is used as a fungicide, insecticide and soil additive to prevent copper deficiencies in crops and animals and to improve crop yields. Biological Action: The activity of copper in plant metabolism manifests itself in two forms: synthesis of chlorophyll and enzymes activity. Although not present in chlorophyll, copper is essential in its production mechanism. The effects of copper deficiency in plants are varied including: die-back, inability to produce seed, chlorosis and reduced photosynthetic activity. Copper is a definite constituent of several enzymes catalyzing oxidation-reduction reactions (oxidases). Copper is also a necessary trace element in animal metabolism. The human adult requirement is 2 mg per day, and the adult human body contains 100-150 mg of copper. A poor copper diet can leads to anemia, diarrhea and nervous disorders. On the other hand, excess of copper compounds such as the sulfate can cause vomiting, cramps, convulsions and even death.
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30. Zinc
History: Zinc ornaments with more than 2500 years have been discovered, but should now be considered as alloys since they have composition of only 80 to 90% zinc, with the remainder lead including iron and antimony as impurities. Its material could not, under modern concepts, be called a commercially saleable metal. The first smelting and extraction of the impure metal was carried out in China and India, around 1000 A.D.. The first slab zinc or spelter was imported from the East in the early seventeenth century, late when compared with iron, copper or lead. The metal did not even have a universally accepted name at this time, being known as tutanego, Indian tin, calamine or spiauter. The term "zink" was first used by Lhneyes in 1697. The commercial designation for zinc from a distillation process is still spelter. Knowledge of smelting zinc was brought from China about 1740, and a zinc smelter was erected in Bristol, England. A patent was granted in 1758 for smelting zinc from a roasted blende or zinc sulfide, fundamentally the present distillation process. The electrolysis process of obtaining of zinc was introduced in USA, by 1916. Occurrence: Zinc is found as a mineral in the earth's crust, usually associated with other base metals such as copper and lead. Zinc deposits are widely distributed throughout the world. The mineral found in massive deposits, where by far the largest tonnage occurs, usually has a high iron impurity content. This ore, known as marmatitic zinc, may have as much as 10% iron with zinc being only 40-45% in the concentrate. The large sources are Canada (British Columbia), USA (Utah, Colorado, Idaho), Peru (Cerro de Pasco Mine) and Australia (Broken Hill). The other common sulfide mineral is sphalerite, found in vein type deposits. The largest producers of this ore are Canada (Ontario and Quebec), USA (Missouri), Peru (Central Andes) and Japan. Applications: Metallic zinc is used in the production of alloys and in galvanizing to protect steel structures. It is still present as a chemical additive in rubber and paints. In the galvanizing process the coating is applied by hot-dip method or by electrodeposition. The latter gives a relatively thin coating that is usually used as a base for paint. Galvanizing is used to protect building structures or boat and machine elements. Brass is one of the most important zinc alloys, and consists of a mixture of this element with copper. It is generally stronger and more ductile than copper. It has superior corrosion resistance and is widely used in water valves, hardware, instruments and communication equipment. Rolled zinc forms part of the container of the common dry cell used to supply electrical current for small portable radios and flashlights. The more important zinc compounds are the oxide (ZnO), used in ceramics, rubber industries and in ink production. Zinc sulfate (ZnSO4) is used in textile industry and the treatment of zinc deficiency in soils. Zinc chloride is used to preserve wood and as deodorant in several fluids. This compound is also used in dry cells and in paint production. Biological Action: Zinc has been found to be as essential element in the growth of humans and animals. It has been proved that a zinc-rich diet promotes fast healing of wounds. In agriculture, zinc compounds are used as a nutritive supplement to promote growth, in addition to their use as fungicides. Zinc is not regarded as inherently toxic. However, zinc oxide, when freshly formed and inhaled, causes a mild disorder known as "zinc chills" or "oxide shakes". Soluble salts of zinc have harsh metallic taste and if taken internally can cause nausea and purging. Inhalation of zinc chloride fumes can injure the lungs and respiratory tract.
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31. Gallium
History: Gallium was discovered in 1875 by the French chemist Lecoq de Boisbaudran. Spectroscopic examination of concentrates from a Pyrenea blende revealed emission lines whose positions corresponded to those predicted for "eka-aluminum", a missing element between aluminum and indium in Mendeleev's Periodic Table of the elements. Boisbaudran subsequently prepared this new element by electrolysis of caustic solutions and observed some of its properties. He named it gallium from the Latin Gallia in honor of his fatherland. Occurrence: A close analog of aluminum, gallium is widespread in the earth's crust. It occurs almost entirely as a hydrated oxide in reconstituted minerals and comprises a rather constant proportion of all aluminum-bearing ores. In zinc and germanium ores, gallium may occur as the sulfide. Its most concentrated deposits (0.5% - 1%) have been found with South African germanite. Gallium has been found concentrated up to 1% in flue dust as a result of the volatility of gallium suboxide. It has also been reported in concentrations up to 0.5% in coal ash. Gallium is not present in significant amounts in the sea or other natural waters because of the very low solubility of the oxide at near neutral pH. Applications: When gallium first became available in the metallic form, it seemed to have properties not found in any other material. It is relatively inert, nontoxic, and with a melting point only slightly above room temperature and a boiling point of 2403 C. It was considered as a liquid sealant in high-vacuum systems, as a heat-transfer medium in high-temperature engines, such as nuclear reactors, and as component of dental alloys. It is somewhat paradoxical that the rather substantial uses of gallium that eventually evolved were based not on unique physical properties of the metal but on the specific chemistry of some of its compounds. The first significant use of gallium was in the spectroscopic analysis of uranium oxide done in operations of the Atomic Energy Commission. The application of gallium that has received the most attention is the production of semiconducting compounds. For many years this technology was dominated by the elemental semiconductors, silicon and germanium. But in 1952, German workers reported the achievement of semiconduction in compounds between elements in group III and group V. Of these, the most important are the compounds of gallium with antimony, arsenic or phosporus. Nowadays gallium arsenide (Ga-As) is undoubtedly the most used. This compound is used in the production of several electronic parts such as diodes and transistors, made for voltage rectification, signal amplification, etc. Other gallium arsenide applications are the semiconductor "lasing" and microwave generation and also in several sensors to measure temperature, light or magnetic field.
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32. Germanium
History: In his report on "The Periodic Law of the Chemical Elements", in 1869, Mendeleev predicted the existence of several unknown elements. Among them was one which was supposed to be just bellow silicon and, for that reason, he called it eka-silicon. Mendeleev studied several minerals, although unsuccessfully, seeking for that new element 32. In the Summer of 1885, it was found in the Himmelsfurst mine (Freiberg, Germany) a new mineral that was called argyrodite. The exact composition of this ore was unknown so that C. Winkler, a Freiberg's chemist, proposed its study. He found silver, sulfur, iron oxide, zinc and an element unknown till that time (eka-silicon). In February of 1886, Winkler was sure of the discovery of this new element that he named germanium in honor of his fatherland. Occurrence: Germanium is not very abundant, so that we can even say that it is a rare element. Its principal compounds are argyridite (4Ag2S.GeS2), germanite (7CuS.FeS.GeS2), canfieldite (4Ag2S.(Sn,Ge)S2) and renierite ((Cu, Ge, Fe, Zn, As)S). Of these only the germanite deposits in Tsumeb (Southwest Africa) and renierite deposits in Katanga (Congo) are of major industrial significance. Trace amounts of germanium (up to 0.3%) are reported in many sulfide and oxide minerals and coal. Applications: Germanium is extensively used in metallurgy and in the production of solid state electronics. Added to beryllium, it leads to increasing ductility, and added to copper, it improves chemical resistivity. It is also used in several brazing alloys. Germanium in the form of GeO2 is an important constituent of industrial glasses because of its infrared transmission and high refractive index. Germanium has played by far the most important role in the development of solid state electronics beginning with the discovery of the transistor in 1948. It is one of the most studied and best understood of all elements. The discovery of the transistor action pointed the way to numerous solid state electronics phenomena which formed the basis of a new science and technology of solid state electronics. It was with germanium that almost perfect single crystals never achieved with other elements were developed. Cyclotron resonance, a means for determining the effective mass of charge carriers, was first observed in germanium single crystals. A variety of optical and magneto-optical measurements allowed for determining of fundamental parameters necessary for understanding the band structure of solids. Nowadays germanium is used in the production of electronic components such as diodes, transistors, light and temperature sensors, etc.
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33. Arsenic
History: Arsenic has been found in Nature since Antiquity. Aristotle makes reference to sandarach (arsenic trisulfide) in the 4th century B.C. In the 1st century A.D., Pliny stated that sandarach is found in gold and silver mines and arsenic (arsenic trioxide) is composed of the same matter as sandarach. By the 11th century three species of arsenic were known, the white, yellow and red - since then recognized as arsenic trioxide, arsenic trisulfide (orpiment) and arsenic disulfide (realgar), respectively. Albertus Magnus is reputed in the 13th century to be the discoverer of metallic arsenic. However, his documentation is considered vague. It was not until 1649 that J. Schroder clearly reported the preparation of metallic arsenic by reducing arsenic trioxide with charcoal. Thirtyfour years later, N. Lemery also observed that metallic arsenic was produced by heating arsenic trioxide with soap and potash. By the 18th century the properties of metallic arsenic were sufficiently known to classify it as semimetal. Occurrence: The terrestrial abundance of arsenic is about 5 grams/ton being found widely dispersed in Nature. Some native samples of arsenic have been found which vary in purity from about 90 to 98%. The commonly associated impurities encountered in these samples are antimony, bismuth, iron, nickel and sulfur. Normally, arsenic is found in Nature combined as sulfides, arsenides, sulfoarsenides and arsenites, and occasionally as oxide and oxychloride. The most commonly encountered minerals of arsenic are arsenopyrite (FeAsS), loellingite (FeAs2), enargite (CuS.As2S5), orpiments (As2S3) and realgar (As2S3). The bulk of the arsenic of commerce, however, is recovered as a by-product from the smelting of copper, lead, cobalt and gold. Uses: Because of its semimetallic properties, arsenic is used in metallurgical applications as an additive metal. Additions of 2% of arsenic to lead assists in the manufacture of lead shot to improve its sphericity. The addition of up to 3% arsenic to lead-base bearing alloys improves both their mechanical and high temperature properties. A small amount of arsenic is added to lead-base battery grid metal and cable sheating to improve the hardness of these materials. In minor additions arsenic will improve the corrosion resistance and raise the recrystallization temperature of copper. In amounts of 0.15 - 0.50%, arsenic improves the high temperature applications of copper utensils. High-purity arsenic is used in semiconductor technology to produce gallium arsenide. This compound finds application in semiconductor devices as diodes, transistors and lasers. Indium arsenide is used for infrared detectors and in Hall effect applications. Small quantities are also used as a dopant in germanium and silicon devices Biological Action: The toxicity of arsenic depends on its chemical state. Metallic arsenic and arsenious sulfides are inert or nearly so, while arsine, AsH3, a gas, is extremely toxic. Arsenical compounds are in general hazardous, principally because of their irritant effects on the skin. Men handling arsenic trioxide industrially wear special clothing and masks which frequently are changed; otherwise, dermatitis may result particularly in the folds of the skin or moist areas. Poisoning by means of inhalation of dusts or fumes are unusual but care should be taken and ventilation should be installed. Most poisoning is due to ingestion.
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34. Selenium
History: Selenium was first identified in 1817 by John Jacob Berzelius, a chemistry teacher in Stockholm. Berzelius and his colleague J. G. Gahn were studying a method of producing sulfuric acid in lead cameras when they observed residues of a substance with a very intense scent in the bottom of the camera. At first, they thought it was tellurium. However, a more careful analysis revealed that there were no residues of this element, in spite of its identical properties. To this new substance was given the name selenium, term that derives from the Greek selene (Moon), for analogy with tellurium, deriving from tellus (Earth). For many years, selenium was just a laboratory curiosity, with no practical application. In 1873, Willoughby Smith discovered that the selenium electrical resistance decreases with increase intensity of incident light. This discover allowed for the development of photoelectric cells and other light sensors. Occurrence: Selenium is a rare element with a particular unpleasant smell and occurs in the native state with sulfur in the form of seleniate in minerals such as eucairite (CuAgSe), claustalite (PbSe), naumanite (Ag2Se), crookesite ((CuTlAg)2Se) and zorgite (PbCuSe). The main selenium sources are copper ores, from which it is recovered as a by-product in the processes of electrolytic refining. The largest world producers are the USA, Canada, Sweden, Belgium, Japan and Peru. Applications: Selenium exists in several solid allotropic forms with colors varying from the dark-red to the black, being the hexagonal crystalline form the more stable under normal conditions. In this form, selenium has properties of a typical semiconductor but its more important electronic property is photocondutivity. For this reason it is mostly used in producing photocells, rectifiers and photographic exposure meters. Besides these applications, selenium and its compounds can be used in the processes of xerographic reproduction, in the glass industry (cadmium seleniate, to produce red-ruby color), as degasifier in the metallurgical industry, as vulcanizing agent, as oxidizer in some reactions and as catalyst. Biological Action: Elementary selenium is not very toxic. However, some of its compounds are extremely dangerous. Concentrations of hydrogen selenate higher than 0,1 milligrams per cubic meter of air, can be quite harmful or even lethal. The exposure to vapors that contain selenium can cause irritations of the eyes, nose and throat. The inhalation of these toxic vapors can be very dangerous.
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35. Bromine
History: Bromine was discovered by two scientists working independently. In the Autumn of 1825, student K. Lowig took a bottle of a reddish liquid with an unpleasant smell to the Laboratory of Medicine and Chemistry of Prof. L. Gemlin, at the University of Heidelberg. Lowig told Gemlin that the liquid, of mineral origin, resulted from the treatment with gaseous chlorine, thus explaining the red color. The substance responsible for that red color was extracted with the help of ether, giving origin to a pink liquid later known as bromine. Almost simultaneously, A. Balard, who was working in a pharmacy school in Montpellier, isolated a substance with the same properties of the liquid obtained by Lowig. At first he thought that it was a chlorine or iodine compound. As he could not isolate the compound, he suggested to have found a new chemical element. Balard suggested the name "muride", from the Latin word "muria" for brine. The French Academy of Science, in turn, proposed the name "brome" from the Greek word bromos meaning stench to indicate its strong irritating odor. Occurrence: Bromine is the twenty-fifth element in order of abundance in Nature. It is so chemically active that it never occurs free in Nature, but always found as a halide. Except for same rather rare silver salts, no natural mineral contains bromine as an essential constituent. There are salt deposits or brines in various parts of the world where bromine has been concentrated by evaporation of water from prehistoric seas or salt lakes. Average ocean water contains 67 mg of bromine per liter, and is the major source of this element. The major world producers of bromine are the United States, Israel and Germany. Applications: The greatest use of bromine is in the manufacture of ethylene bromide which enters in antiknock fluids for motor fuels. Lesser amounts of bromine are used to prepare a great variety of other organic and inorganic compounds. Bromine is an excellent bleaching and sanitizing agent and, as a liquid, is used as a reagent for analytical and synthetic purposes. The pure cesium bromide so obtained has been used in manufacturing optical prisms which are highly transparent to infrared radiation. The bromides of the alkali and alkaline earth elements find usage in pharmacy because of their sedative actions, in photography for preparing silver bromide emulsions, and in the industrial drying of air as desiccants. The major use for methyl bromide lies in the extermination of insect and rodent pests. Bromochloromethane and bromodifluoromethane are used as fire-extinguisher fluids. Biological Action: Liquid and gaseous bromine presents a serious health hazard. The liquid rapidly attacks the skin and other tissues to produce irritation and necrosis. Exposure to vapors can cause painful irritation to the eyes and inflammation of the respiratory tract. The maximum concentration which is considered safe for an eight-hour exposure is less than 1 PPM. Plants for the manufacture or use of bromine should be designed to provide maximum safety precautions and good ventilation. Many bromine compounds have important physiological applications and are therefore employed in Medicine as sedatives, anesthetics and antiseptics.
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36. Krypton
History: Krypton was discovered in May 1898, in the residues resulting from of the evaporation of great amounts of liquid air used to prepare argon. In fact, this element was discovered by chance, when Ramsay and Travers decided to do a fractional distillation of liquid air when trying to isolate the neon, unknown at that time. They centered their attention in the heaviest fraction and, purifying it of possible nitrogen sludge and oxygen that could still exist, observed its spectrum. They were extremely surprised with a bright yellow line, that did not belong to the helium or to the sodium, revealing the presence of an unknown gas. This new gas was denominated krypton, from the Greek word "hidden" due to the circumstances of discovery. Occurrence: We can find krypton in Nature almost exclusively as constituent gas of the atmosphere, where it is present in a concentration in the order of 0,00011% for volume of dry air. It is also present in small concentrations in some natural gases and in gases that emanate from thermal waters and from the volcanoes. It is the second rarer element in the terrestrial crust (considering oceans and atmosphere), where it is present in concentrations similar to those of xenon. Applications: Due to its rarity, krypton does not have many applications. Its main commercial use is in the illumination industry, where, together with argon, is used in fluorescent lamps, since it increases its shine and improves the tubes efficiency. Krypton is also used in flashes for high-speed pictures, because it allows an emission of a very intense light in a very reduced time (this gas, when excited, emits an intense flash that lasts only 1/50000 of a second). In smaller amounts, the element can also be used in incandescence lamps to increase the life of the tungsten filament. It can also be used in Medicine as absorber of X-ray or anesthetic.
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37. Rubidium
History: Rubidium was discovered by Kirchhoff and Bunsen, in 1861, when they noticed the existence of new spectral lines in a lepidolite sample. Its name derives from the Latin "rubidus" (dark-red), due to the zone of its spectral lines. The preparation of the metal was tried by Bunsen, but he never got samples with more than 18% of rubidium. The separation of the metal was only accomplished by Hevesy, through the hydrolysis of melted rubidium hydroxide. Later, Hevesy also obtained rubidium through the reduction of that hydroxide sodium, potassium or hot aluminum. Occurrence: Rubidium is widely distributed throughout the terrestrial crust. It is a relatively abundant element when compared to lead, copper, zinc or cesium. No minerals have rubidium as the main constituent. However, some potassium ores contain compounds of the element, such as the Rb2O, present in the lepidolite, amazonite, leucite, pollucite, petallite, beryl or biotite. In the carnallite it is possible to find 0,035% rubidium chloride. One can also find rubidium in common rocks as granite, basalt and several clays, or still in ocean and natural spring waters. Due to its widely distribution, the extraction is very complex and expensive. Applications: Many of its salts are hygroscopical and corrosive, and should be handled with precautions. The element has limited applications, being important its use in vacuum tubes and photocells. Rubidium carbonate is sometimes used in the glass industry. It is also extensively studied as a potential heat transmission material in space vehicles, as fuel in motors of ionic propulsion, as electrolyte in low temperature alkaline batteries, etc. Some rubidium compounds are used in preparing soporific, sedatives and in the treatment of epilepsy. Biological Action: There is evidence of some degree of toxicity of rubidium for humans. In experiences with animals, the inclusion of the element in the diet can cause neuromuscular hyperirritability symptoms and reproductive deficiencies. In extreme cases it causes violent muscular spasms or even death. By skin contact, metallic rubidium causes serious cutaneous burns, in spite of the fact that most of its compounds only slightly irritate the skin. The most toxic rubidium compounds are the fluoride, the hydroxide and the cyanide.
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38. Strontium
History: Strontium was first detected by Crawford in Edinburgh, in 1790, although some authors credit the discovery of the element to William Cruikshank, also Scottish, in 1787. Both used the ore strontianite (SrCO3), extracted from a lead mine located in Strontian, Scotland. According to other versions, Kirwan and Klaproth are the discoverers of the element, in 1793. These chemists analyzed strontianite, and found a carbonate of a new earth, which would be called strontia. The metal was only isolated by Sir Humphrey Davy, in 1808, through the electrolysis of a mixture of strontium hydroxide with mercury oxide. Occurrence: Strontium is not as abundant as calcium or barium. It can be found in minerals as the cellestite (that contains SrSO4) and the estroncianite (that contains SrCO3), both relatively abundant in the terrestrial crust, being the first the more common form. Strontium is also found in small amounts associated with other rare-earth minerals. The main deposits of these minerals are found in the USA, the United Kingdom, Germany and Mexico. Applications: Strontium does not have direct applications as a pure metal. However, its compounds can be commercially used, as it is case of the carbonate (SrCO3) and of the oxide (SrO), used in the sugar industry, or the nitrate (Sr(NO3)2), used in pyrotechnics, fireworks preparation and signal or alarm fires, because it produces a bright red flame. Strontium sulfide is used in beauty treatments and in the production of luminescent paints due to its specific properties. The bromide and the iodide have applications in Medicine, although limited. Biological Action: Strontium plays a similar role to that of calcium in the human metabolism, so it is not toxicant. However, the natural isotopes Sr-89 and Sr-90 are extremely dangerous once ingested, because they take the place of calcium in the bone structure. They are a source of internal radiation and could damage the bony medulla and the blood cells formation, leading to cancer. The bromide and the chloride are used in Medicine to control certain nervous disturbances. Other compounds of this element are used in treating rheumatism.
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39. Yttrium
History: Yttrium was discovered, in 1794, by the Scandinavian chemist Johan Gadolin, through the treatment of an ore obtained in Ytterby, Sweden. This small city would give the name to this element as well as the others obtained from the same ores, as terbium, erbium and ytterbium. Yttrium was isolated for the first time in its metallic state, in 1828, by Wohler. Although it is not a lanthanide, it is frequently considered to belong to the rare-earth family, due to the likeness of both its chemical and metallurgical properties. For a long time there were no applications of the element, due to the difficulty of separating from the rare earth. However, with the recent improvement of these techniques, its study has been deepened, revealing new applications. Occurrence: Yttrium occurs, in the terrestrial crust, associated to the rare earths due to its common geochemical origin. As a phosphate, yttrium occurs in the mineral xenotime and monazite, and as silicate in the gadollinite and as columbate in the samarskite. Other minerals with considerable amounts of yttrium are fergusonite, apatite, blomstrandite and euxenite. These ores are generally called yttrium earths. The main deposits of these minerals are located in Norway, USA, Canada and Brazil. Yttrium is present in the terrestrial crust in concentrations of no more than 40 ppm. Applications: Yttrium is quite used in producing alloys, optical glasses and ceramics. It is also used in special catalysts and in opto-electronic devices such as lasers, filters for microwaves and "europium phosphorus" for the red color in television sets. Some of its isotope are radioactive being used in cancer radiotherapy. Biological Action: The properties of this element are not very well known; however, we cannot consider it toxic.
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40. Zirconium
History: Zirconium was discovered as zirconium oxide in 1789 by Klaproth who worked with the mineral zircon (ZrSiO4), zirconium silicate in the form of semiprecious gemstones from Ceylon. Such zircon gems derive their name from the Arabic zargun (gold color) and Klaproth named the element zirconium. J. J. Berzelius first produced the metal in 1824 in impure form by the reduction of K2ZrF6 with potassium. The first ductile metal of good purity was made by the reduction of resublimed zirconium tetrachloride with high-purity sodium, first by Lely and Hamburger in 1914 in Germany and later in the early 1920's by Cooper and Hunter in the USA. In 1925, van Arkel and de Boer applied their iodide decomposition process to make very pure zirconium. Occurrence: The mineral zircon, zirconium orthosilicate, is the only commercial source of zirconium used nowadays. It is found in alluvial deposits, ocean beaches and old lakebeds throughout the world. In Australia, ocean beaches are mined for rutile and at the same time provide the most important source of zircon. A second important source of zircon results from mining of ilmenite in old beach deposits in Florida. There are at least 35 known minerals of zirconium, most of which have no commercial significance. Baddeleyte (zirconium dioxide) is an important zirconium ore that can be found mostly in Brazil. Applications: The most important zirconium compound, the zircon, is used as refractory material for mould-casting, as abrasive and as constituent of insulating materials, enamels and other resistant to the temperature materials. It is also used as an artificial semi-precious stone, imitating diamond. Zirconium oxide is used as refractory material in the production of piezoelectric crystals and rings of high frequency induction reels, due to its low resistance to high temperature. It is still used as pigment in the ceramic industry. More than 80% of the produced zirconium is consumed in the form of these two compounds. Other zirconium compounds have interesting properties and important applications. Thus, the carbide and the nitride with their high hardness, are used in producing abrasives and sharp edged instruments; the hydride is an hydrogen source and can be used as moderator in nuclear reactors; the double ammonium carbide and zirconile are used in preparing hydrophobic fluids and water-proof coatings; the phosphate, the molybdate and the tungstate are used as ion permuters, especially selective for alkali metals. Metallic zirconium is the best construction material for nuclear reactors due to its low neutron cross section, high mechanical and chemical resistance and appropriate thermal conductivity. It is also used in the manufacture of zircaloy alloys that contain tin, iron and chromium in small amounts. Other smaller applications include flash production for photography, explosive, fireworks, tracer bullets, small rockets, etc. Biological Action: Zirconium has a very low order of toxicity so that no restrictions are necessary for control of health hazards. The major hazard to be considered in the use of the metal results from its high tendency to combine with oxygen at relatively low temperatures in spontaneous and exothermic reactions. For this reason, powder and fine dusts explode when dispersed in air and should be handled with extreme care.
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41. Niobium
History: In 1801, C. Hatchett found an unknown ore at the time during the analysis of some chromium minerals from Connecticut. He called this mineral "columbite", and the corresponding element "columbium", because it had been discovered in an American mineral. One year later, in 1802, A. G. Ekeberg discovered a new element in Finnish minerals similar to the columbite and named it "tantalum". This name derives of the god Tantalus, of the Greek mythology, in allusion to the enormous difficulty to dissolve the mineral in acids. In 1844, H. Rose found two new elements in a sample of columbite of Bodenmais. They were similar to the Ekeberg's tantalum and were called "niobium", in honor of Niobe, mythological daughter of Tantalus and goddess of the tears. Sainte-Claire Deville and Troost made the distinction between tantalum and niobium, and determined the formulas of some of its compounds. The columbium of Hatchett was probably a mixture of these two elements, although the term has been used later on as synonymous of "niobium". Blomstrand prepared the metal for the first time in 1866 by reduction of niobium chloride with hydrogen. Occurrence: Niobium can be found associated with tantalum in ores which are rich in rare earths. Up to 1950, this element was extracted almost exclusively of the mineral niobite, in occurrence with pegmatitic rocks. Since then large resources of niobium have been discovered as the carbonates. The major deposits of this element are in Brazil, Nigeria, Canada and USA. Applications: Niobium tends to form borides, silicides and numerous inter-metallic compounds, some of them with notable superconducting properties as the Nb3Sn. These compounds have high electrical resistivity and reflectivity and small volatileness, what makes them ideal in induction ovens or in radiation shielding. The metal is used in the production of iron-niobium alloys, and of other more complex alloys that can be applied in the construction of propulsion turbines and in rockets and space ships.
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42. Molybdenum
History: The name molybdenum derives from the word used by the Greeks, molybdos, for galena and other lead ores. Until the middle of the 18th century, it was supposed that molybdite or molybdenite were identical to graphite, then known as "plumbago" or "black lead". In 1778, K. W. Scheele, in its "Treatise on Molybdena", showed that, unlike the graphite, the molybdenite formed a "peculiar" white earth when treated with nitric acid. He proved that it had acid properties and called it "acidum molybdenae", which means, molybdenic acid. He also considered that the molybdenite mineral was a molybdenum sulfite. Later, in 1782, P. J. Hjelm isolated the element, in the form of a metallic powder, by heating up molybdenic acid with charcoal. In 1893, German chemists obtained the metal with 96% degree of purity and, the following year; Henri Moissan reached 99,98% by reduction of the element in an electrical oven. The first register of an alloy made with molybdenum dates from 1894. Occurrence: The metal does not occur free in Nature. Its principal ores are the molybdenite, the molybdenum disulfide, that can be found in the USA (Colorado), in Canada (Britannic Colombia) and in Chile. Other minerals with possible industrial interest are the powellite (Ca(MoW)O4) and the wulfenite (PbMoO4). Molybdenum can also be obtained as secondary product during the tungsten extraction. Applications: Molybdenum is used in the production of steels and special alloys, with high resistance and hardness, hard to melt and resistant to attacks from chemical agents. They are particularly useful in the production of pieces and devices subjected to high strains in unfavorable use conditions. It is the case of the gas turbines, reaction motors, trunnions, rolling supports, supermagnets, etc. Among other applications, we should refer the use of its disulfide as solid lubricant, similar to graphite. The metal and some of its organic-metallic compounds are used as catalysts in the production of gasoline with high octane. An important part of the world production is still used in the coloring industry and in inorganic pigments. Biological Action: Several studies on acute toxicity of molybdenum revealed that it is biologically inoffensive. The molybdenum is considered by some scientists as essential in animal nutrition, although a daily minimum amount has not been established yet. The iron sulfate with molybdenum was used for a long time to prevent anemia in pregnant women. Nowadays one considers that a rich in molybdenum diet contributes to healthy dental enamel.
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43. Technetium
History: Technetium is a radioactive element discovered in 1937 by C. Perrier and E. G. Segr in Palermo, Italy, during the study of the by-products of deuteron bombardment of metallic molybdenum. On the basis of powder diffraction patterns carried out by Mooney on material supplied by Parker, it was later shown that technetium fits into the Periodic Table between manganese and rhenium because of its similarity in crystal structure type. Occurrence: All the isotopes of technetium are radioactive. The long-lived isotopes are still too short to allow the existence of primordial technetium in the earth's crust. Yet, technetium has been detected in some stars, and theories of stellar evolution and element synthesis must explain its presence there. Applications: The metal and its compounds have naturally very few applications. The pertechnetate anion (TcO4-), possesses anticorrosive properties. This corrosion protection is available only in closed systems since the technetium must be confined because of its radioactivity. Technetium and its alloys are superconductors with critical temperatures of the same order as niobium and its compounds, and they can be used to create magnetic fields of high strength in compact units at low temperature. The short-lived Tc-99m isotope has found extensive use in clinical medicine. It is used to locate tumors in the spleen, liver, brain and thyroid by scintillation scanning. Biological Action: Due to the radioactivity of the element, the maximum allowed concentrations are measured in radioactive activity (Ci - 1 Curie), which represents the number of decays per time unit. The maximum permissible concentration of Tc-99 in water is 0,01 Ci/cc and in the air is 2x10-6 Ci/cc. In the human body, the maximum permissible burden is 10 Ci in the kidney, 20 Ci in the liver, 400 Ci in the skin, 500 Ci in the bone and 2000 Ci in the lungs. Even though Tc-99 has a long half-life and emits only weak 0,29 MeV beta radiaction, it is still considerable contamination hazard, and should be handled in a glove box.
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44. Ruthenium
History: Ruthenium was the last of the platinum metals to be discovered. In 1824, extensive alluvial deposits of native platinum were discovered in the Ural Mountains, in Russia. Very soon Russia became the main producer of that metal, developing and improving its metallurgical industry. Various scientists, such as G. W. Osann, of the University of Dopart, were in charge of the study of the insoluble residues of the platinum. He announced, in 1828, that this material contained three new elements which he named pluran, ruthen and polin. In spite of this research, some of his work was not considered by some famous chemists like Berzelius, but was inspiring to some others like K. K. Klaus leading to the discovery of ruthenium in 1844 in the University of Kazan. The name of the element was proposed by Klaus and it derives from the latin name " Russia ", major producer of these metals and in recognition of the work of Osann. Occurrence: Ruthenium always occurs associated to other platinum metals, being its abundance comparable to the one of the rhodium and of iridium. The main world producers of platinum metals are Canada, South Africa and Russia. The abundance of the element in the terrestrial crust is estimated to be 0,001 grams per ton. Applications: Ruthenium is used in the hardening of platinum and palladium in the metallurgical industry. It is also used in electrical contacts with high resistance to corrosion, in the production of dental alloys, in protecting coatings against oxidation and in the production of high mechanical resistance accessories. Palladium alloys with 4,5% of ruthenium are used in jewelry and ornaments. When added to titanium, it improves considerably the corrosion resistance. Noteworthy is its use as catalyst in the hydrogenation process of carbonyls.
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45. Rhodium
History: Rhodium was discovered, in 1804, by W. H. Wollaston, working in London at the time. Wollaston made a partnership with Smithson Tennant, in 1800, with the goal of developing and improving the technology of platinum refining. To one of the native platinum shipments from South America was applied an elaborated treatment. Mercury cyanide was added to the aqua regia platinum solution, the precipitate was removed and the resulting solution was evaporated. The residues were washed with alcohol, and the result was a dark-red material that was proved to be a sodium compound and a salt of a new metal. That salt would today be known as sodium chlorodite (Na3RhCl6.18H2O). This salt was heated up with hydrogen and was washed with water to remove the sodium chloride. The resulting residue was rhodium powder. Wollaston chose the name rhodium (from the Greek rhodon, that means rose) due to the color of the chloride RhCl3 and of the respective aqueous solutions. In 1885, Le Chtelier developed the first rhodium-platinum thermocouple, following a suggestion of Becquerel referring to the possibility of using the rhodium thermo-electric effect to measure temperature. Occurrence: Rhodium occurs invariably associated to other platinum metals. The major deposits of rhodium are located in the north of Siberia (Russia), in Ontario (Canada), and in Transval (South Africa). The extracted ores in Canada are rich in nickel and copper sulfide while those extracted in South Africa have volcanic origin, being rich in pyroxene. Other mineral deposits that contain rhodium, although of smaller commercial importance, result from the erosion of primary deposits and is found in Russia, Colombia and in Alaska. The rhodium abundance in the terrestrial crust is about 0,001 grams per ton. Applications: Rhodium is mainly used in the production of alloys with the platinum, with resulting high hardness and resistance materials. These alloys are used in electric ovens in glass industry, in turbine reactors, in the production of thermocouples and in catalytic nets for different chemical reactions, in particular the oxidation of ammonia into nitric oxide. The metal also finds some application in jewelry for the coating of silver objects, in the production of projectors, in the production of emitting and receiving circuit components, etc. In jewelry, rhodium is used as a fine film coating of white gold jewels, by electrolytic deposit. This process improves the aspect of the jewel, turning it very white and more resistant.
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46. Palladium
History: In 1800, Wollaston made a partnership with Smithson Tennant for developing and improving the technology of platinum refining. These scientists worked for over 15 years in the treatment of South American ores. The first step of the purification process was the addition of aqua regia to the imported mineral. The precipitate compound was then removed and the resulting solution was initially thrown away. However, Wollaston studied this solution leading to the discovery of palladium, in 1803, and of rhodium, in 1804. Wollaston added mercury cyanide to the solution and got an yellowish precipitate. After several purification processes he washed the residue and obtained a white metal. This new element was named palladium in honor of the newly discovered asteroid Pallas. Occurrence: Palladium is almost invariably associated with other platinum metals. The major deposits of rhodium are located in the north of Siberia, in the Ural mountains, in the Ontario region of Canada, and in Transval in South Africa. Other mineral deposits that contain palladium, although of smaller commercial importance, are located in Colombia and Alaska, USA. Palladium, like all the platinum metals, occurs in volcanic rocks like peridotite or norite. In Siberia, palladium occurs associated to iron, nickel and copper sulfides. The palladium abundance in the terrestrial crust is about 0,01 grams per ton. Applications: Palladium is applied in the electrical industry in the production of electromechanical contacts as relays. In the chemical and pharmaceutical industry it is used as a catalyst of hydrogenation reactions and in the oil industry palladium is very important in the catalysis distilled petroleum fractions. The element is also applied in some alloys used in dental medicine. In jewelry palladium is hardened with a small fraction of ruthenium or rhodium, and can be used as decolorizing agent of gold, creating the so-called white gold.
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47. Silver
History: Silver is known by the mankind since Pre-History, and its discovery is estimated happened to shortly after that of copper and gold. The oldest reference to the element appears in the book of Genesis. The Egyptians considered gold to be a perfect metal, and gave it the symbol of a circle. Since silver was the closest to gold in perfection, it was given the symbol of a semicircle. Later this semi-circle led to a growing moon symbol, probably due to the likeness between the shining metal and the moon glow. The Romans called silver argentum, keeping this as the international name of the element, from where its chemical symbol derives. Just as gold, silver was considered by the Ancients an almost sacred metal and consequently, of extremely restricted use. Its malleability and ductility make it ideal for ornamental purposes. It was also used for paying debts, in personal and religious places decoration and in utensils of the wealthiest houses. Some mineral scums in old mines of the Near-East and in some islands of the Aegean sea seem to reveal that by 5000 b.C. a method was already known to separate silver from lead. The gold and the silver were extracted from its ores and bonded to lead. After oxidation of this mixture, it was possible to obtain the precious metals. Occurrence: The main silver mineral is the argentite (Ag2S), which usually occurs associated to other sulfides as copper or lead sulfide. Other silver minerals are cerargirite (AgCl), proustite (3Ag2S.Ag2S3), pirargirite (3Ag2S.Sb2S3), stefanite (5Ag2S.Sb2S3) and native silver. The silver occurs in most of the lead and copper ores, and associated to cobalt and gold arsenide. Most of the produced silver is a by-product of the extraction process of these metals. However there are some mines specially devoted to the extraction of this element. The largest world producers of silver are the USA, Canada, Mexico, Bolivia, formerUSSR, Australia and Germany. Applications: The most important silver inorganic compound is, undoubtfully, the nitrate, because it is used in almost all the processes of production other compounds. Silver nitrate has a wide application in painting, xerography, chemical electroplating, in components for electric batteries and in Medicine as catalyst. Silver chloride is another important compound, due to its ductility and malleability. The organic compounds of the element are used in the coating of several metals and in dynamite or other explosive bars. The most important alloy of this element is silver-copper, traditionally used in producing coins. Nowadays this alloy was replaced by a cheaper alloy, copper-nickel. There are other silver alloys used in producing radiators for the automobile industry, and in producing musical instruments. The chemical industry uses metallic silver as catalyst of several oxidation reactions such as those of ethanol and other alcohols. The oil industry also uses silver nitrate as catalyst. For many years, the mirrors were made by deposition of a small silver coat on a glass surface. Nowadays aluminum is used for this purpose. Biological Action: Silver is a non-toxic element. However, most of its salts are poisonous due to the presence of its anions. These compounds are absorbed by the body and remain in the blood stream until they are deposited in the mucous membranes, forming a greyish film. However, there are some silver compounds, like the nitrate, with an antiseptic effect. Solutions of silver nitrate are used in treating irritations of mucous membranes in the mouth and throat. Some proteins that contain silver are powerful anti-irritating agents of the membranes of the eyes, heard, nose and throat.
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48. Cadmium
History: Cadmium was discovered in 1817 by F. Strohmeyer, a professor of metallurgy at Goettingen, Germany. While investigating some zinc carbonate, Strohmeyer found that the compound, upon heating, was yellow instead of white, and he concluded from further tests that the color was due to a previously unknown oxide. Separating some of this metallic oxide from the zinc carbonate by careful precipitation with hydrogen sulfide, he subsequently reduced it to metal. Strohmeyer named the metal cadmium from "cadmia", a term for calamine (zinc carbonate) At about the same time K. S. Hermann separated a similar sulfide from some Silesian zinc ore and sent it to Strohmeyer, who identified it as the sulfide of the same metal which he had just discovered. Occurrence: Cadmium is a relatively rare element. Its abundance in the lithosphere is estimated at about 0.5 parts per million in the earth's crust. No cadmium has been found in commercial quantities, and no ore is mined solely for recovering cadmium. The most common mineral, greenockite (cadmium sulfide), occurs chiefly as a yellow stain or coating on zinc sulfide. Nearly all major zinc deposits contain cadmium in varying amounts, with the concentrates containing a maximum of about 1%. Applications: The major use of cadmium is for plating articles to form a protective coating (mainly on iron and steel); most of this plating is done by electroplating. An in important use for cadmium is in the nickel-cadmium storage battery. Cadmium is used in many alloys such as bearing metals, solders, electrical conductor, fusible metals and jewelry. Cadmium absorbs low energy (thermal) neutrons readily; and, when rods of cadmium are inserted in a nuclear reactor, this absorption of thermal neutrons provides a means for controlling the fission process. In the electronics industry, cadmium is used in television phosphorus and in photovoltaic cells, radiation detection devices, infrared windows, and photosensitive devices. Biological Action: Cadmium is one of the most toxic metals. The main route of absorption of cadmium in industrial exposure is by inhalation, therefore, industrial processes which generate cadmium dust or fume should be well ventilated. A single exposure to high concentrations of freshly generated cadmium oxide fume can cause severe pulmonary irritation and even death.
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49. Indium
History: Indium was discovered in 1863, by the physics professor F. Reich and his assistant T. Richter at the Freiburg School of Mines, while they were checking local zinc ores with a spectrograph for thallium. After several attempts, Reich obtained a precipitate that he knew to be a sulfide of an unknown element. He used than several spectrographic techniques to identify the new element. However, Reich, suffering from daltonism, asked for help to his assistant T. Richter, for doing the spectral analysis. Richter observed a bright blue stripe, unknown in any other spectrum and distinct from the blue stripe of cesium. To this new element was given the name indium because of the bright indigo blue spectral stripe. Metallic indium was first obtained in 1867,by T. Richter. Occurrence: Indium does not occur in the native state. It is widely distributed in Nature although generally in low concentrations. The Earth has been estimated to contain 0.1 ppm of indium, about the same abundance as silver. It is found in many ores including those of iron, lead, copper, tin and particularly zinc. Like many of the rarer metals indium becomes concentrated in by-products during recovery of the major metals. The occurrence of indium has been reported in several countries, including Canada, Finland, Germany, Italy, Japan, Peru, Sweden, USA and ex-URSS. Applications: The major application of indium is in automobile bearings to improve moisture resistance and antiseizure properties. It is also used in the semiconductor industry. In this application, indium acts as a doping agent in the formation of p-type germanium. Examples are transistors, diodes and rectifiers The most important indium alloys are indium-tin, lead-indium-silver and copper-silverindium, all used as solders. Indium is also used in plating applications due to its electrolytic properties, and in the production of electroluminescent panels, as an oxide. Biological Action: Indium is considered a non-toxic element, never being reported any serious accident with this element. Even in welding or semiconductor industry, where the exposition to indium is relatively high, there is no report of any kind of toxicity
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50. Tin
History: Tin is one of the oldest metals known by man. There are domestic utensils and arms made of brass (copper with about 15% of tin), dating from 3500 b.C.. The Phoenicians had a very important role in the spread of brass utensils due to its commercial trades with Britain, Spain and the Middle East. Pliny referred, in 49 a.D., to the existence of tin and lead alloys, what we now know as solder, as well as recipients of tinned copper. Tinned iron was only developed in the 14th century in Bohemia, and tinned steel appeared only in the 17th century. Originally confined to Britain and Spain, the tin extraction spread throughout to other countries of the Southern Asia and to Congo, Nigeria and Bolivia. Occurrence: The major producers of tin are Malaysia, Thailand, Indonesia, Bolivia, Republic of Congo, Nigeria and China. Although in a smaller scale there are also tin deposits in Australia, England, Burma, Japan, Canada, Portugal and Spain. The only tin mineral with commercial importance is the cassiterite (SnO2). This ore does not occur in mineral veins but in extensive alluvial deposits where the concentration does not surpass 4%. Applications: As a pure metal, tin is used in the production of electronic valves, and in the production of recipients for distilled water, beer and carbonated drinks. It can still be used in storage tanks for pharmaceutical chemical solutions, in capacitors electrodes, fuse-wires, ammunitions, tinned iron sheets to protect victuals, sweets or tobacco etc. The tin powder is used in the production of these papers and of inks and sprays. Electro-plating is another important application of tin. It can be done through the electroplating of a small coat of tin around objects of steel, copper, aluminum etc. The tinned pieces have countless applications such as in kitchen utensils, spray recipients and shaving foam, ink cans, electronic components, integrated circuits, clips, pins and many other. Tinned objects can also be used with ornamental purposes. The more important tin compounds are the tin dioxide (SnO2), used in electric resistors and dielectrics, and the tin monoxide that it is used in the production of tin salts for electroplating and as chemical reagents. The tin compounds that contain lead, barium, calcium and copper are indispensable in the production of electric capacitors. The tin fluoride is used as addictive in tooth-pastes. Some of the tin organic compounds have several application as fungicides and insecticides for the agriculture and still as wood, textile and paper preservers. Biological Action: Only a small tin amount passes to victuals due to the use of tin utensils. The maximum allowed amount in victuals is about 300 mg per kilogram, but in spite of this, higher concentrations are not, in general, harmful. Tin can be considered as a non toxicant element. However, some of its compounds have toxicant properties and should be handled with extreme care.
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51. Antimony
History: Antimony in the form of its natural sulfide was known to the ancients and was used by them as cosmetic and medicine. The Old Testament refers to its use by Jezebel as a cosmetic for the eyes. The early Egyptian women also adorned their eyes with antimony sulfide as evidenced by its presence amongst the articles discovered in the ancient tombs. Pliny in his writings during the 1st century a.D. describes seven remedies that can be obtained from the use of stibium (antimony sulfide). Metallic antimony was mentioned in the early works of Dioscorides written in the 1st century a.D. The art of producing metallic antimony was well known by the 17th century. Basil Valentine described its preparation in his work Triumphal Chariot of Antimony probably written in 1350 a.D. but published in 1604. Libavius in 1615 described the use of iron to reduce stibnite directly to metallic antimony. Lemery in this book Cours de Chemie published in 1675 also describes methods for its preparation. There is no doubt that the metal was well known to the artisans of the Middle Ages. The name antimony was obtained from the Latin term antimonium which first appeared in a Latin translation of the work by Ceber. Occurrence: The terrestrial abundance of antimony is about 1 gram/ton compared to about 5 grams/ton for arsenic. Over one hundred minerals of antimony have been recognized. Scattered quantities of native metallic antimony are found in Nature, however these are rare. The most important mineral source of antimony is stibnite, antimony trisulfide. Stibnite deposits are normally small and shallow, and do not contain more than several thousand tons of ore. Ore bodies of this nature can be found scattered throughout the world and are located in Algeria, Bolivia, China, Mexico, Peru and ex-Yugoslavia. Other important commercial minerals of antimony are stibcontite, cervantite, valentinite, senarmontite and kermasite (2Sb2S3.Sb2O3). Complex ores of antimony such as livingstonite (HgSb4S7) and jamisonite (Pb2Sb2S5) are also a source of antimony. Antimony is also present in copper and lead in minor quantities, but has sufficient value to be recovered as a byproduct element. Another important source of antimony is from the treatment of lead-base scrap material. About one-half of all antimony produced is derived from this secondary scrap source. Uses: Antimony is used metallurgically as an additive element since the physical properties of the element are not suitable for engineering applications. Its most important use is as an alloying constituent for lead and lead-base alloys to impart hardness and stiffness, and to improve the corrosion resistance. It is also used as an alloying ingredient for tin alloys to produce pewter, and tin-base babbits for bearing metal applications. The element is also used in cable covering, castings, solder, etc. The trioxide is used in the preparations of medicine, in dye mordants and for staining dull finishes on iron and copper hardware. Antimony sulfide is used in vulcanizing rubber, as a vermilion pigment and other pigment shades such as yellow, formed by slow oxidation of the sulfide, and the blue by mixing the yellow with other pigments. It is also used to a lesser extent in fireworks, ammunition primers, tracer bullets and metals. Semiconductor Applications: Antimony of purity exceeding 99,999% is used in semiconductor technology. This material may be produced by the reduction of high purity compounds such as trioxide and chloride with hydrogen. Important III-V compounds such as AlSb, InSb and GaSb are made from high purity antimony. These compounds may be used as infrared detectors, diodes and Hall effect devices. The compound in this group with the biggest technological importance is InSb. Antimony with a purity of 99,99 % is an important alloying ingredient in Bi2Te3 - type alloys which can be used as thermoelectric coolers or power generators.
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Biological Action: The toxicity of antimony depends upon its chemical state. Metallic antimony is relatively inert, while stibnite is highly toxic. The toxicity of other compounds of antimony may be classified between these extremes. In handling antimony and its compounds proper ventilation should be used in order to avoid atmospheric contamination. Cases of dermatitis have been reported in the manufacture of antimony trioxide.
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52. Tellurium
History: Tellurium was discovered in 1782, by Franz Mller von Reichenstein after several studies of a blueish gold ore, extracted in a mine in Transilvania. Mller accomplished a careful chemical analysis of this ore, and reported residues of a metal very similar to antimony. However, Mller was not able to identify this metal. It took over a year to consider this hypothesis. The metal was isolated, in 1798, by Klaproth that was interested in the work of Mller, as he was decided to check the existence of a new element. This scientist suggested its actual name , that derives of the Latin "tellus", that means earth. Occurrence: Tellurium is a not very abundant element, and can be found associated to the gold, copper or sulfur ores. The element occurs in small amounts in minerals like the altaite (PbTe), the calaverite (AuTe2), the coloradoite (HgTe), the ricardite (Cu4Te3), the petzite (Ag3AuTe2), the silvanite ((Ag,Au)Te2) and the tetradimite (Bi2Te2S). Tellurium can also be found in the native state and in the dioxide form (TeO2). The main tellurium deposits are located in Canada, in the USA (Montana, Utah and Arizona) and in Peru. Applications: Tellurium has been used in metallurgic industry to improve the mechanical properties of steels and other ferrous alloys. It is also used in the form of alloys with copper and lead, used in welding works and in chemical equipment. In the rubber industry, tellurium is used to improve its properties such as its heat resistance. This element can still be used as catalyst. As some of its binary compounds, tellurium can be used in the production of thermoelectrical devices used in power plants and refrigeration. These applications are based on the Seebeck effect, for the current production when heating up a junction of two different metals, and in the Peltier effect that consists of heat transfer by means of an electrical current flow through a metallic junction. Biological Action: Tellurium is slightly less toxic than selenium. The main tellurium intoxication symptoms are vertigo, nausea, headaches, sleepiness being also observed an unexpected dryness of the mouth and a strong breath, extremely unpleasant. This can be minimized by the ingestion of ascorbic acid (vitamin C). Tellurium is eliminated by the body through the lungs, the urine, the feces and the sweat. There is not any record of acute intoxications caused by this element. However, it should always be handled with care.
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53. Iodine
History: Iodine was discovered in May 1811 by the French chemist, Bernard Courtois, who manufactured potassium nitrate for Napoleon's armies. In Courtois' process calcium nitrate, isolated from nitre beds, was converted to potassium nitrate by means of potash from wood ashes. In order to conserve potash much of the nitrate was converted to sodium nitrate by means of crude ash which was obtained from kelp (seawood ashes). While washing the kelp with sulfuric acid to destroy certain impurities. Courtois noticed violet fumes which condensed and corroded his copper equipment. Properties of this new substance were investigated by F. Clement and J. B. Desormes and later by J. L. Gay-Lussac, who first recognized it as a new element and named it after the Greek word for violet. Since its discovery, iodine has been a major factor in the advance of chemical technology. Its importance in the development of synthetic organic chemistry is exemplified by Hofmann's researches on the reactions of alkali halides with ammonia and the amines, and Williamson, Wurtz and Grignard, in the advent of the 19th century. Occurrence: Iodine is widely distributed in Nature, occurring as iodides or iodates but never as a free element. It is usual to find iodine in rocks, soils and underground brines. Seawater contains about 0.05 ppm. Less than a dozen minerals in which iodine is an essential constituent have been found being the most important lautarite and calcium iodate, found in Chilean nitrate deposits. Despite the low concentrations of iodine in seawater, some seaweeds, notably of the brown variety, accumulate iodine on a dry basis. Applications: One of the oldest and largest uses for iodine is in the disinfectant area. An almost universally known product is "tincture of iodine" for household disinfectant use. Certain iodides have found use in the catalyst system for producing stereospecific polymers such as polybutadiene rubber. Also the dehydrogenation of butane and butylene to butadiene has been shown to be catalyzed by iodine that is also useful in polymer production. Other applications of iodine are as food supplements, X-ray contrast media, radioactive tracers, photographic processing chemicals, constituent of cutting fluids use in heavy machinery. The element is also used in metallurgy with titanium, silicon, zirconium and hafnium. Biological Action: Courtois' discovery of iodine in seaweed ash in 1811 apparently constitutes the first reference to iodine as a plant substance. The amount present in land varies from 10100g per 100g of dry matter. The seaweeds richest in iodine contain 10 000 times more iodine. Further studies of the iodine content of plant and animal foods arose from the discovery in 1895 that iodine is a normal constituent of the thyroid gland. The major cause of goiter is iodine deficiency in soil, food and water. In endemic goiter areas which have existed in many parts of the world the addition of one part of NaI or KI to 100 000 parts of NaC used as tablesalt appears quite satisfactory in the prevention of the disease. The isotopeI-131, with an eight day period, is a useful radioactive tracer in particular on the study and treatment of thyroid cancer.
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54. Xenon
History: Xenon was the last noble gas to be discovered. In the sequence of several studies made by William Ramsay and M. W. Travers, in 1898, and as a result of the krypton purification by fractional distillation, it was obtained an extremely dense gas that those two scientists were unable to identify. The spectroscopic analysis of that gas revealed that was a new element that was named xenon. This name derives from the Greek word xenon that means "strange". Occurrence: Xenon occurs in Nature as a constituent element of the atmosphere, in an amount of 8,6 x 10-6 % per volume of dry air. This gas is heavier than krypton and less abundant than its precessores in the group of the noble gases. Its abundance is considered to be about 2,9 x 10-9 % in the terrestrial crust (including oceans and atmosphere). Most of existing atmospheric xenon has primordial origin. However, it is considered that the amount induced by the uranium and thorium fission is about 0,5%. Applications: Xenon has very little applications due to its high cost and limited abundance. It is used in photography flashes and in the proportional counters filling gas mixtures for radiation detection, due to its high cross-section of ionization by X-rays or gamma rays. Historically it is important to refer the old use of xenon in certain bubble-chambers. The xenon compounds have very limited applications; however, some of them can be used in analytic chemistry as oxidizing agents and fluorizing agents for specific purposes. Biological Action: Xenon can be used as anesthetic in human surgery due to its narcotic behavior. This property is directly related to its high solubility in fat nervous tissue. Although xenon can affect the human metabolism it is not considered toxic. However, its compounds are quite noxious due to its strong oxidizing properties.
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55. Cesium
History: It was discovered in 1860 by Kirchhoff and Bunsen while examining the residues that were obtained by evaporation of mineral waters. The new bright lines in the blue region were attributed to a new element - given the name cesium for the Latin caesius - sky blue. Extraction of cesium compounds by Bunsen involved concentration of the cesium and other impurities by evaporation of large volumes of mineral water. Bunsen prepared chlorides, carbonates and other salts of cesium. He studied the properties of these salts and attempted to prepare cesium metal but was unsuccessful. The metal was first obtained by Setterburg in 1882 by electrolysis of a cesium cyanide-barium cyanide melt. Cesium had no significant industrial application until 1926 when the metal was used as a getter and an effective means for reducing the electron work function on coated tungsten filaments in radio tubes. Occurrence: Cesium is widely distributed in Earth's crust al very low concentrations. Granites, sea water, and sedimentary rocks contain less than 5 ppm cesium. Mineral springs contain as much as 9mg/l of cesium. Higher concentrations of cesium are found in certain potassium minerals such as the micas, beryl, feldspar, petalite. Some other minerals such as biotite, amazonite, lepidolite or carnalite contain residual concentrations Only two cesium minerals are known. These are pollucite, a cesium aluminum silicate, and rhodizite, a borate of aluminum, beryllium, sodium and cesium. The most important deposits of these minerals are located in the United States (South Dakota and Maine), Canada (Manitoba), Southwest Africa (Karib) and Zimbabwe (Bikita). Applications: Metallic cesium is used in photoelectric cells and infrared detectors, because of its property of being readily ionized by light energy. The most important cesium compounds are the hydroxide, the carbonate, the iodide and the bromide. Cesium hydroxide is used as an electrolyte in alkaline storage batteries for use in subzero climates. Cesium carbonate has been used in specialty glasses. The iodide and bromide are used in some scintillation counters because they emit electrons when exposed to radiation. Cesium bromide is also used to measure the epitaxial film thickness of semiconductors The atomic clock uses cesium as the time measuring element based on the precise movement of its outer electrons. Biological Action: Cesium has been shown to have a pronounced physiological action on animals when administrated in amounts equivalent to potassium. Hyper-irritability including spasms were found eventually leading to death. Cesium metal can cause serious burns when it comes into contact with the skin. Its extreme reactivity with moisture and oxygen requires it to be handled with extreme care. The toxicity of cesium compounds is generally of very minor importance except when cesium is combined with another toxic metal or radical. Such an example would be cesium cyanide or cesium gallium sulfate. Cesium-137 is used in radiation treatments, for instance in cancer therapy.
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56. Barium
History: It was a Bolognese shoemaker, V. Casciorolus, that noted, in 1602, the phosphorescence of the combustion products of an heavy spar. He called this stone solis-pencil, and this later would come to be called Stone of Bologna. It was thought at the time that this heavy spar was some kind of gypsum. In 1774, K. W. Scheele discovered that this mineral contained a new earth that originated an insoluble sulfate in water. G. of Morveau called it barote, from the Greek barys (heavy), due to the high density of some of the compounds of this element. This name was later changed by Lavoisier being nowadays known as barite. Occurrence: Barium constitutes 0.4 - 0.5% of the Earths crust. The most common barium minerals are barite or barytes which contains BaSO4, and witherite with the carbonate BaCO3. Barium minerals are heavy. For this reason is also known as heavy spar. The high density of barite permits its ready separation from clay and other material associated with many barite deposits. Uses: There are very few uses for barium metal. Thin films of barium are used as a lubricant on the rotors of anodes in vacuum X ray tubes. The most important barium compounds are the carbonate, the nitrate, the oxide and the sulfate. Barium carbonate is used in chemical applications, in the treatment of salt brines to remove some sulfate, as flux in ceramics and as an ingredient in optical glass and fine glassware. Barium nitrate (Ba(NO3)2) is used to produce a green color in flares, pyrotechnic devices and tracer bullets. Barium oxide is used in the manufacture of lubricating oil detergents. Barium sulfate as a paint pigment and in cosmetics. A small but vital use is in X-ray photography of the gastrointestinal tract where it provides a fine opaque contrasting medium ingested prior to X-ray examination. Biological Action: All of the soluble compounds of barium are poisonous when taken by mouth. Although insoluble, barium carbonate is extremely toxic, so as the chloride. The barium ion is a muscle stimulant being very toxic to the heart and may cause ventricular fibrillation. Symptoms of barium poisoning are excessive salivation, convulsive tremors, rapid pulse, high blood pressure, paralysis of the arm and leg, hemorrhage and eventually cyanosis and death. The antidote for ingested poisonous barium compounds is to drink a solution of sodium sulfate which converts the barium to the insoluble harmless barium sulfate.
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57. Lanthanum
History: Lanthanum was discovered in 1839 by C. G. Mosander in Stockholm, Sweden. Mosander partially decomposed a sample of cerium nitrate by heating and treating the resulting salt with dilute nitric acid. From the extracted solution, it was possible to isolate a new rare earth which Mosander called lantana, which means "hidden". The experimental work with the lanthanum was prolonged for the three following years, although the results remained unpublished. For more than one century any important applications for this element were not found. The interest for lanthanum was just scientific, being limited to the investigators improving its separation techniques and purification and knowing its spectrum. Although possessing an electronic configuration different from the one of the lanthanides, it is included in this series due to the likeness of properties that presents with these. Occurrence: The rare earths are never separately extracted, once they form composed inorganic complex. Lanthanum is relatively abundant in the terrestrial crust and estimated to about 18 grams of the element for ton. The minerals that contain lanthanum are monazite, bastnasite, allanite and cerite. Monazite is a rare-earth thorium phosphate and its main deposits are in India, USA, Brazil, South Africa and Australia. Bastnasite is a rare-earth fluocarbonate that contains about 40% of lanthanum. The main deposits of this ore are located in California and in New Mexico. Allanite and cerite are silicate of several elements, including lanthanum. The most important deposits are located in Sweden. Applications: Pure lanthanum has very few applications being almost limited to the scientific research. In spite of this, the metallurgical industry is the only commercial domain where the metal finds application. Lanthanum is sometimes added to other elements such as sulfur, oxygen and hydrogen or ferrous alloys to obtain cleaner metals. In general, the addition of a small amount of lanthanum to steel, improves its malleability, resistance to the impact and ductility. The addition of 0,2 to 5% of lanthanum to molybdenum decreases the hardness of this metal and its sensitivity to temperature variations. Biological Action: It is proven that the injection of lanthanum solutions produces glycohemia, low blood pressure, degeneration of the spleen and hepatic alterations, in the animals. The element is not absorbed orally, and when injected its elimination is very slow. The lanthanum compounds cause ocular irritations in the conjunctive and opacity of the cornea after a latency period of some hours. The exposition to lanthanum vapors induce irritation and refines the senses of the palate and of the smell. Some rare-earths chlorides, such as lanthanum chloride (LaCl3), are known by its anticoagulant properties although they should be used with very care. Lanthanum salts are generally considered to have low or moderate toxicity.
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58. Cerium
History: The element cerium, in the form of an oxide, was "discovered" in 1930 simultaneously and independently by Klaproth and by Berzelius and Hsinger. The name ceria, which was proposed in honor of the newly-sighted asteroid Ceres, was given by Berzelius and Hisinger. This name was accepted by the scientific community of the time. Thirty-six years later, however, Monsander showed that the oxide isolated by these researchers was composed of at least two oxides, for one of which he retained the name ceria and the second he called lanthana, which subsequently was shown to consist of not only lanthana, but also praseodymia and neodymia. Metallic cerium was first isolated by Mosander in 1825 by reducing cerous chloride with sodium. It should be noted that the term cerium is used quite loosely, since Mosander's material contained other rare earths which had not yet been isolated and identified. In the succeeding following years several other investigators prepared metallic cerium by a metallothermic technique, but it was not until 1875, that Hillebrand and Norton prepared cerium by electrolysis of fused chlorides. Today, these are the two most important methods used to prepare metallic cerium. Generally speaking, the metallothermic technique is used to prepare high-purity metal, while the electrolytic method is used to prepare many of the commercial cerium-based alloys. The discovery of the electronic transformation in metallic cerium wherein at least a greater portion of the 4f electron is transferred to the valence level, is contemporary history. A transformation in cerium, in which a large volume (about 10%) occurs, was observed by Bridgman (1948) at high pressure and by Trombe and Fex (1943) at low temperature. Further studies showed that, in spite of this volume change, cerium keeps its structure. Zachariasen (1949) and Pauling (1950), working independently, suggested that the valence of metallic cerium changes from about 3 to about 4 when either cooled or compressed. Presently there is a great deal of research, both experimental and theoretical, being carried out on metallic cerium to better characterize its electronic behavior in the various polymorphic modifications. Occurrence: Cerium is the most abundant element of the rare earth group. It ranks 28th in the abundances of the 83 naturally occurring elements of the Earth's lithosphere. The more important minerals containing cerium are allanite (also known as orthite), bastnasite, cerite, and monazite. Allanite, which is a silicate containing rare earths, aluminum, calcium, and iron, is widely in the United States, Germany, Greenland, Madagascar, Russia and Scandinavia. Bastnasite, which is essentially a rare earth fluorocarbonate, is the second most important commercial source for cerium and the light rare earths. The major deposit of bastnasite is found in Southern California. Cerite, which is a calcium-iron-rare earth silicate, is principally found in Sweden. Although it is quite high in rare earth content, it is not abundant enough to a primary source of the light rare earths. Monazite, which is the principal source of cerium, is a phosphate containing thorium and the light rare earths. The most important deposits are located in the United States (Florida and Idaho), Australia, Brazil, India and South Africa. Applications: Commercially, ceric oxide is the most important form of cerium. There are also many other applications in which mixtures of cerium, lanthanum, neodymium, and other rare earths are used. These mixtures may be of the form of metallic alloys, mixed oxides or mixed halides, etc. Ceric oxide is used to polish glass, especially precision optical glasses. It is superior to rouge, in that it polishes glass much quicker. Because of its oxidizing power, cerium is used in glass which is subjected to alfa, gamma, x-ray, light and electron radiation. The cerium decreases the rate of discoloration in glass, primarily by preventing divalent iron from forming, i.e. oxidizes Fe(II) to Fe(III). This is especially useful in TV tubes, where electron radiation could cause the glass to discolor and destroy the color quality of the TV picture. Cerium dioxide is also used to opacify enamels, photochromic glasses, ceramic coatings, refractory oxides, phosphorus, cathodes, capacitors and semiconductors, and as catalyst.
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Because of cerium's low nuclear cross section, cerium dioxide is used as diluent in uranium, plutonium or thorium oxide nuclear fuels. The most common form of cerium-rare earth alloys is known as mischmetal, and it contains about 50% of cerium, 25% of lanthanum, 18% of neodymium, 5% of praseodymium and 2% other rare earths. It is produced in tonnage quantities by the fused salt electrolysis of a mixture of anhydrous chloride of rare earth element derived from monazite or bastnasite. An increase in the high temperature strength and creep resistance is noted by mischmetal additions to magnesium alloys. It is also reported to increase the strength of aluminum, the oxidation resistance of nickel and nickel alloys, and the hardness of copper with only a slight decrease in the electrical conductivity of the copper. A 30% iron, 70% mischmetal is a common alloy used as lighter flints. The desirable pyrophoric properties of this alloy are due primarily to the cerium. Cerium is also used as getter in vacuum tubes and as diluent in plutonium nuclear fuels. Mixed oxides and fluorides containing cerium are used as cores for carbon arcs. The rare earth mixture increases the intensity about tenfold while improving color balance of this white light. The mixed ceric-rare earth oxides are also used as catalysts for cracking petroleum, as polishing materials and waterproofing agents, and fungicides in textile manufacturing. Biological Action: Most of the biological, biochemical, pharmacological and toxicological studies on cerium have been carried out on small animals. Oral administration of cerium or cerium compounds, unless the anion is toxic, has very little or no effect. This is primarily due to the fact that very little cerium is absorbed by the body. Subcutaneous injection gives a greater absorption. The excretion of cerium, however, is slow, About 50% of the cerium absorbed is deposited in the liver and 25% in the skeleton, and the elimination half-lives are about 15 days and about 14 months, respectively. Cerium was found to produce granulomas from intradermal injections. Intraperitoneal administration of cerium in concentrations of 0.01%, 0.1% and 1% in the diet for 90 days had no effect on the liver. Inhalation of the oxide and/or fluoride induces granulomas in the lung. Cerous chloride and ceric ammonium nitrate stimulate secretationin in low doses but suppress it in high doses. Cerium, like all of the rare earths, decreases the blood pressure and serves as an anticoagulant agent. The rare earths, including cerium, have a low acute toxicity rating.
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59. Praseodymium
History: Auer von Welsbash was the first scientist to isolate the didimia, in 1885, by fractional crystallization of the double ammonia nitrates of two new elements. It was thought at the time that didimia was a simple element. However, Welsbash proved that this substance was a neodymium and praseodymium mixture. Its name derives of the greenish color of the respective salts. Occurrence: Like most rare-earths, praseodymia occurs in relatively high amounts in ores like monazite (a thorium and rare-earth phosphate), cerite (a rare-earth silicate) and allanite (a rare earth, calcium and iron aluminosilicate). It can also be obtained as a by-product of uranium, thorium or plutonium fission. The minerals that contain monazite can be found in India, Brazil and USA (Florida and South Carolina); cerite mainly occurs in Sweden and allanite in the Western USA. The relative abundance of praseodymium in the Universe is very similar to that of rhodium, silver, antimony, thallium or bismuth, and slightly less than the ones of cerium and neodymium and greater than the one of gold. However, if we consider only the Earth crust this concentration can be much higher. Applications: Just like other rare earth elements, praseodymium is used as catalyst in a wide variety of metallurgical applications, in matches, lasers, masers, in industrial glass production, as polishing agent and still in electronic and thermoelectric components. There are no extensive applications of pure praseodymium or of its salts.
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60. Neodymium
History: In June of 1885, the baron Von Welsbash announced, in the Academy of Sciences of Vienna, the separation of the didimia in two new rare-earths, through repeated fractionation of the ammonium didymium nitrate. He proposed the names praseodymia (green twin) and neodymia (new twin) for these new compounds. In spite of the skepticism of many chemists, Robert Bunsen, an old teacher of Welsbash, recognized the legitimacy of this separation. Nor neither the neodymia nor the praseodymia were decomposed in simpler oxides. Occurrence: The lanthanide series is divided in two different groups: the elements with atomic number from 57 to 63, that constitute the cerium group, also known as light rare-earths; and the group of the elements of atomic number from 64 to 71, that it is known as the yttrium group, or of the heavy rare-earths. During the period of rock formation, Nature distinguishes these two groups. The neodymium usually occurs associated to the elements of the cerium group. The neodymium is quite abundant in the terrestrial crust, reaching 0,0024% or 23,8 grams per ton. It is more common than other metallic elements as platinum, mercury, beryl, lead or cobalt. The metals of the rare-earths does not occur freely, but as cations in complex compounds. This element is present, in significant amounts, in four distinct minerals: the monazite, the bastnasite, the allanite and the cerite being the two first the major industrial sources of the element. Monazite is a thorium and rare-earths phosphate, with a monoclinic structure that occurs in granites and in marbles. After the erosion, the monazite is deposited by sedimentation in fluvial beds. The main deposits of this mineral are located in India, Brazil, Idaho, Florida, North and South Carolina, South Africa and Australia. However, the minerals of United States are not sufficiently rich to justify the extraction of rare-earths. The typical percentage of neodymium in the monazite varies between 9% and 20%. Bastnasite is a rare-earth fluocarbonate that contains 2 to 15% of neodymium. In 1949 a large bastnasite deposit was located in California, being other deposits of commercial importance also known in New Mexico. The mineral that contains silicates of rare-earths, calcium, iron and aluminum is called allanite. This mineral is widely distributed through the western United States. There is no wide scale process to extract allanite. Cerite is a mineral that contains calcium and iron silicates, with about 50 to 70% of cerium group elements. This mineral occurs mainly in Sweden, however scarce and only with historical interest. Applications: Little use was made of the elementary neodymium, from its discovery date to the end of the forties. The chemists were quite busy, trying to improve the separation and purification techniques, to determine its properties, its spectrum and its reactivity. Even with the fast and extensive progresses in the rare-earth technology in the last decades, very few applications for neodymium were found. Biological Action: Investigators have found that the injection of rare earths in animals (mice, rats and rabbits) has pronounced effects. The injection of neodymium salts induces the hepatic cirrhosis, decreases the blood pressure, causes hyperglycemia and spleen degeneration. Direct contact of these salts with the eyes cause a severe irritation, and are necessary about three weeks for a total recovery. Direct contact with the skin does not produce any damage or irritation. In humans, neodymium vapors cause an increase to the heat sensibility, itching and a sharper sense of the taste and smell. The rare-earth chloride act as anticoagulants, to decrease prothrombin and heparin, but have produced undesirable side effects. Neodymium nicotinate is a more active, less toxic anticoagulant. Antibacterial effects have been observed with didymic acid application to cultures. Neodymium salts are rated as having a low-to-moderate acute toxicity. Mixtures of rare earths appear to be worse than the individual elements and intravenous inoculations can be
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lethal to animals. The dominant effects caused are both lung and skin granuloma with local inhalation or injection.
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61. Promethium
History: Promethium was the last of the rare-earths family elements to be discovered in Nature. It was only in 1965, and after innumerous attempts to isolate the metal from natural ores, that O. Erametsa was able to obtain about 20 tons of rare-earths starting from 6000 tons of apatite. From these, he isolated a small fraction of 350 milligrams of a radioactive element which he thought to be the isotope 147 of the element with atomic number 61. However, the discovery of the element is attributed to J. A. Marinsky and L. E. Glendenin, that, in 1945, identified the 147-Pm in the byproducts uranium fission. The element was isolated three years later in Oak Ridge Laboratory (USA) by G. W. Parker and P. M. Lantz. The metal was prepared for the first time by F. Weigel in the University of Munich, in 1963. Applications: Once there are no stable isotopes of this element, it has been quite difficult to find commercial applications to this element. However, its use in luminescent inks for counters and pointers of clocks, and as source of X-rays should be pointed out. Biological Action: The main inherent danger of this element is its radioactivity. Therefore, there must be special care in handling the element, avoiding direct exposure and recurring to the use of appropriate clothes (for example lead gloves should be used to manipulate thin films that contain promethium), etc.
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62. Samarium
History: The discovery of samarium is attributed to Boisbaudran, who accomplished the separation of samaria from a rare-earth (cerium and lanthanum) mixture called didymia, obtained by Mosander in 1879. In fact, the Boisbaudran's samaria was a samarium and europium mixture, separated in 1901 by Demarcay. The denomination samarium derives from the name of the ore smarskite, named after the Russian officer Samarski. Occurrence: The samarium represents about 1 to 2% of the rare-earth that naturally occur in the earth crust. However, sometimes is possible to find ores where the samarium abundance reaches up to 7%. The main ores with commercial interest for extraction of rare-earths are monazite and bastnasite, which contain about 2% of Sm2O3. Monazite is a rare-earth orthofosfate, and can be found in India, Sri-Lanka, Brazil, Australia, USA and South Africa. Bastnasite is a rare-earth fluorcarbonate, and occurs mainly in California. Applications: Samarium and its compounds do not a wide variety of applications. However, one can stress out the use of samarium oxide in the production of sun glasses and glass filters, to increase the infrared absorption and as a catalyst in some chemical reactions. On the other hand, titanate can be used to stabilize the performance of electric capacitors. Biological Action: The toxicity of samarium is not very well known. The handling of this metal should thus be made with care.
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63. Europium
History: The discovery of europium is generally credited to Demarcay who obtained the earth in pure form in 1901 by fractional crystallization of double magnesium nitrates, although as early as 1892 Boisbaudran had obtained basic fractions from samarium-gadolinium concentrates having spark spectral lines not accounted for by samarium or gadolinium and subsequently shown to belong to europium. The scarcity and complex chemistry of europium undoubtedly accounted for its late discovery, coming over 15 years after the isolation of samarium. The name, of course, is taken from Europe. Occurrence: The rare earths as a group constitute about 0.008% of the Earth's crust and europium generally comprises from 0.05 to 0.2% of the rare earth mixture. The principal commercial ores from which rare earths are extracted are monazite and xenotime, each being rare earth phosphates, and bastnasite, a rare earth fluocarbonate. Monazite, a rare earth-thorium orthophosphate is found in many countries such as India, Brazil, Australia, South Africa and the United States, occurring as placer deposits on the beaches as the result of weathering and gravity concentration. It can be obtained as a by product from ilmenite, rutile, zircon and staurolite. Bastnasite is a rare earth fluocarbonate, the largest deposit being located in the Mountain Pass region of California. Applications: Up until 1964 europium was used primarily as a neutron absorbing component of control rods in nuclear reactors. Even here the use was limited due to the high cost and total consumption was relatively small. The real impact on the rare earth industry came with the announcement of the development of a new red phosphorus for color television: europiumactivated yttrium orthovanadate to replace the silver-activated zinc-cadmium sulfide. After this consumption of europium and yttrium has increased in relation to the enormous growth of the color television industry. Biological Action: The toxicity of europium is unknown. Care must be exercised in handling the metal due to its reactivity, particularly with respect to spontaneous ignition in finely divided form.
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64. Gadolinium
History: The discovery of gadolinium is generally credited to the Swiss chemist Marignac, who isolated the element from Mosander's yttria in 1880. It was independently discovered in 1885 by Boisbaudran who isolated the from Mosander's "didymia", a mixture of rare earths from which the cerium and lanthanum had been extracted. It was named in honor of the Swedish chemist Gadolin. Elemental gadolinium is a metal resembling steel. It is active chemically as evidenced by its reaction with dilute acids to give the corresponding nitrates, chlorides, etc. Occurrence: The two most important ores from which rare earths are extracted are monazite and bastnasite. Monazite is a rare earth-thorium orthophosphate usually found in sand beach platters in deposits located in India, Ceylon, Brazil, Australia, USA and South Africa. Bastnasite is a rare earth fluorcarbonate and the largest deposits are located in California. Both monazite and bastnasite contain residual amounts of thorium oxide (ThO2) which is responsible for the radioactivity of these ores. Applications: A number of uses for gadolinium have been found; its uses have not been as large as those of others lanthanides. The element is used as shielding in nuclear applications due to its high thermal neutron absorption cross section. It is also used in control rods in nuclear power plants. The largest single use of gadolinium is as a partial substitute for yttrium in yttrium-iron garnets where it stabilizes the characteristics of the garnet with respect to temperature. A solid solution of neodymium and gadolinium oxides has exhibited properties useful as a thermoionic emitter. Biological Action: The toxicity of gadolinium is unknown. Some care must be exercised in machining the metal to prevent hot chips from igniting.
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65. Terbium
History: The professor of Chemistry and Mineralogy of the Caroline Institute, in Stockholm, Carl Gustav Mossander showed, in 1843, that the oxide denominated yttria could be decomposed in three rare earths, which he called: yttria, a colorless oxide; erbia, a yellow earth; and terbia, a rosy earth. He separated these earths by fractional precipitation with hydroxide ammonia. On the other hand, the professor of Chemistry, at the University of Geneva, Jean Charles Galissard of Marignac separated terbia from yttria, but changed the names of the oxides, calling terbia to the erbia of Mossander. This denomination is still valid today. The terbia received its name in honor of the Swedish city of Ytterby. The almost pure elementary substance was first prepared by G. Urbain, in 1905. The metal can be obtained by reduction of the terbium trifluoride with metallic calcium. Terbium is one of the rarest of the lanthanide series and therefore with very little commercial applications. Occurrence: Terbia constitutes about 1% of the mineral xenotime, a phosphate of rare earths, and about 1,3% of the mineral euxenite, a complex oxide. Xenotime is magnetically separated from the deposits of monazite of Florida and South Carolina. On the other hand, euxenite can be found in extensive deposits in Idaho.
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66. Dysprosium
History: The element was discovered in 1886 by Lecoq de Boisbaudran and was named dysprosium after the Greek word dysprositos, meaning hard to get at. Neither the oxide not the metal were available in good quality until the development of adequate ion-exchange separation and metallographic reduction techniques by Spedding and co-workers at the middle of the 20th century. Occurrence: Dysprosium is the most abundant of the heavier (yttrium group) lanthanide elements and is approximately as abundant as arsenic, hafnium and uranium. The more important mineral sources of dysprosium include xenotime, gadolinite, euxenite, samarskite, fergusonite, blomstrandine, polycrase, loparite and yttroparisite. Xenotime occurs in Norway, Sweden, Brazil, Malaysia, Korea, Switzerland and USA. Gadolinite occurs in Norway, Sweden, Masagascar and USA. Euxenite is found in Australia, Brazil, Canada, Finland, Madagascar, Norway and USA. Fergusonite is found in Greenland, Norway, Sweden and USA and samarskite in Madagascar, North Carolina and Ontario. Polycrase is found in Norway, Sweden and North and South Carolina. Loparite and yttroparisite are found in Russia. Since it is processed commercially for uranium, thorium and yttrium, euxenite is a prime source of dysprosium. This element can also be obtained as a by-product in the processing of monazite. Applications: Dysprosium has been recommended as a possible consumer poison in reactor fuels and has been used in metallic foil form to measure flux. Dysprosium has also been employed as a fluorescence activator in some phosphorus. Biological Action: Dysprosium has a low acute toxicity rating, but soluble salts injected intravenously cause some degeneration of liver and spleen. .
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67. Holmium
History: The element was discovered in erbia by J. L. Soret and M. Delafontaine in 1878 by means of its spectrum. Soret named the new element X. By 1879, P. T., Cleve had independently shown that Marignac's erbia was a mixture of at least three oxides, those of erbium, holmium and thulium. He named one fraction holmia after his native city, Stockholm. This faction was later found to have the same spectrum as X. Holmia was not isolated into a reasonably pure compound until 1911 following the work of O. Homberg and others. Between 1911 and 1945, a great deal of work was done on fractionating processes to separate pure holmium from other rare earths. The metallic form of the element was produced in a powder form mixed with KCl by W. Klemm and H. Bommer in 1934. They reduced the anhydrous chloride with potassium vapor. During the late 1940's and early 1950's separation methods were developed at the Ames Laboratory which carried out these fractionation processes automatically. At the present time, a number of industries are using ion exchange techniques to prepare pure holmium, and it can be obtained in high purity in commercial quantities if desired. Occurrence: The rare earths are widely distributed throughout the earth's crust in extremely low concentrations. They also occur concentrated in numerous minerals but always as mixtures of all the rare-earths, along with lanthanum, yttrium, thorium and other elements. The amount of a given rare earth varies greatly from mineral to mineral, but the heavy rare earths are usually present in low concentrations. Holmium is one of the less abundant of the rare earths; however, it has been estimated to be present in the earth's crust to about 12 parts in ten million. It is, therefore, more abundant than antimony, mercury, iodine or bismuth. The more important sources of holmium are the yttrium-rich mineral - xenotime, gadolinite, euxenite and fergusonite, to mention a few. In these minerals, holmium is present in concentrations up to 1%. However, holmium also occurs as a trace impurity in many minerals such as apatite, bastnasite and monazite, where it is present from 0.001% to 0.1%. Monazite and some of the other rare-earth minerals are processed extensively for cerium, lanthanum, thorium and yttrium, and the by-products of some of these processes are now the principle sources of holmium. Biological Action: The toxicity of various holmium salts has been studied. When inhaled, taken orally, or injected into the blood stream in massive amounts, holmium salts can cause serious damage. However, the conclusion is to classify the rare earths as having a low acute toxicity rating. Since their effect in low concentrations on humans over long periods of time has not been determined, these materials should be handled with reasonable care.
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68. Erbium
History: In 1794, J. Gadolin discovered a new element in a heavy black mineral (gadolinite) which he had found near Ytterby, Sweden. He obtained about 38% of the new oxide from the mineral. This new oxide was called yttria. This same oxide was isolated from a number of other minerals, In 1842, C. G. Mosander found that this oxide was complex and that it could be resolved into three fractions - the most basic one, which he called yttria, the least basic one, erbia, and the intermediate one, terbia. All of these rare earth oxides were named after the town of Ytterby, Sweden, near where the first mineral was found. Yttria was white and gave colorless salts, erbia was orange-yellow and gave colorless salts, while terbia was white and gave rosecolored salts. Mosander's results were confirmed by several other chemists, but during this early period of rare-earth chemistry, the names erbia and terbia became confused so that Mosander's terbia became erbia after 1860 and his erbia was known as terbia after 1877. Mosander's intermediate fraction, now called erbia, was later shown to be complex and resolved into a mixture of five oxides: erbia, rose-colored; sacandia, white; holmia, tan; thulia, white; and ytterbia, white. By 1905 G. Urbain and C. James had independently succeeded in isolating fairly pure erbia. The metallic form of the element was produced in a powdered form mixed with KCl by W. Klemm and H. Bommer in 1934. They reduced the anhydrous chloride with potassium vapor. During the late 1940's and early 1950's separation methods were developed which carried out these fractionation processes automatically. At the present time, a number of industries are using ion exchange techniques to prepare pure erbia, and it can be obtained in high purity in up to ton quantities if desired. Occurrence: The rare earths are not really rare in that they are found in the parts per million range widely distributed throughout the earth's crust. They always occur as mixtures of all the rare earths, and these mixtures are frequently found concentrated in numerous minerals. The relative abundance of the rare earths varies from mineral to mineral, but in general the heavy rare earths are always present in minor amounts. It is estimated that erbium occurs in the earth's crust to about 24 parts in ten million. Erbium is more abundant, therefore, than bromine, iodine, antimony, mercury and cadmium. Applications: Highly pure individual rare earths at reasonable prices have not been available commercially for a sufficient time to allow large scale industrial uses to be developed. It is already clear that the rare earth, and particularly erbium, play an important role in laser production and development, in the electronics industry and in some sensing instruments. However the most important use of the heavy rare earths is as powerful tools used by scientists to obtain a better understanding of chemical, physical and metallurgical principles and to obtain a clearer picture of the nature of matter. Biological Action: The toxicity of various erbium salts has been studied. When inhaled, taken orally, or injected into the blood stream in massive amounts, erbium salts can cause serious damage. However, the conclusion is to classify the rare earths as having a low acute toxicity rating. Since their effect in low concentrations on humans over long periods of time has not been determined, these materials should be handled with reasonable care.
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69. Thulium
The thulium, of atomic number 69, can be considered as a smaller "element". However, its physical and nuclear properties made it technologically useful. Thulium is obtained from thulium oxide (Tm2O3), as a result of the yttria production by ion exchange. History: The element was discovered in 1879, by Cleve, and was called thulium from Thul, the northest inhabited region in the world. However, it was only isolated in form of pure thulia in 1911, by James. Due to its low natural abundance, thulium was never truly available in a pure state (for example, more than 99,9% of Tm2O3) in amounts in the order of a gram, nor prepared in a metallic form, until the 50's when Spedding and its co-workers developed the techniques of reduction by ion exchange. Occurrence: Thulium is the less abundant of the rare-earths (excluding promethium). However, it is sixtieth fifth in abundance among the constituents of the earth crust. It is, in fact, more abundant than some of the most common elements as cadmium, silver, indium, palladium, platinum, gold, selenium, etc. The most important sources of thulium are the minerals rich yttrium: xenotime, gadolinite, euxenite, samarskite, fergusonite, blomstrandine, loparite and yttroparisite. However, small amounts of thulium can be found in many common rocks and minerals like apatite and monazite, that also contains cerium. The minerals rich in yttrium are occasionally found in pegmatites in spite of being more frequent when associated to monazite. Xenotime occurs in Norway, Sweden, Brazil, Switzerland, Malaysia, Korea, North and South Carolina and in Colorado. Gadolinite can be found in Sweden, Norway, Madagascar, Texas, Arizona and Colorado. Euxenite occurs in Finland, Brazil, Norway, Australia, Madagascar, North Carolina and Idaho. Fergusonite is found and extracted in Greenland, Sweden, Norway, North and South Carolina and in Texas. Samarskite occurs in Madagascar, North Carolina and Ontario. Blomstrandine in Norway, luparite and yttroparisite in Russia. Of these minerals, the xenotime and the gadolinite are the ones most easily treated through chemical reaction, originating the pure concentrates of rare-earths. Euxenite is also an important thulium source due to its role in the uranium, thorium and yttrium extraction. Applications: Thulium will probably never be produced at reasonably low prices, due to its low relative abundance and separation difficulties. An important application of the thulium in the Medicine area, and relatively independent of its high cost, is the production of portable X-ray sources. These sources are available for about one year, as tools in medical and dental diagnosis, as well as to detect defects in mechanical and electronic inaccessible components. This type of sources does not need excessive protection. Usually a small cap of lead is enough. Thulium can also be used in magnetic and ceramic materials (ferrite), similar to the yttrium-iron alloys, nowadays used in the microwave technologies. Biological Action: The rare-earths, including thulium, have very low toxicity. However some lingering effects due to the repeated intravenous injection have been reported, including liver and spleen degeneration, as well as fluctuations in the hemoglobin concentration. The damages in the liver due to the thulium ingestion (0,01 to 1% of the diet) are more prominent in males rather than females, according to experiences performed with mice.
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70. Ytterbium
History: Ytterbium was discovered by J. C. G. of Marignac, in 1878, as an impurity in erbium oxide. The fraction of ytterbium isolated by Marignac contained small amounts of scandium and lutetium. The name of the element derives from the name of the Swedish city Ytterby and its feldspar extraction mine. It was in this mine that the ores containing the first discovered rareearths were extracted. The metallic ytterbium was isolated for the first time by Klemm and Bommer, in 1937, through the reduction of its tricloride with potassium. However, this sample was too impure, and it was only in 1953 that gram amounts of metallic ytterbium were prepared. Daane, Denison and Spedding got a sample, free of impurities, that used to study its physical and chemical properties. Occurrence: Ytterbium is one of the less abundant rare-earths. This element is slightly less abundant than boron, molybdenum and thallium, but slightly more abundant than antimony and tantalum. The main ores that contain ytterbium are euxenite, gadolinite, monazite and xenotime. Euxenite is a complex titanium-niobium tantalic that contains small amounts of thorium and uranium. The main deposits of this mineral can be found in Idaho. Gadolinite contains a beryl and iron silicate, and occurs mainly in Scandinavia. Monazite is a complex phosphate that contains thorium and vestiges other rare earths. This mineral is the most important source of the element. The most important deposits are located in Florida, Idaho and also in Australia, Brazil, India and South Africa. Smaller deposits occur in Egypt, Malawi, Sri Lanka, Indonesia, Malaysia, Korea, Uruguay and Argentina. Xenotime is a rare earth that occurs associated to monazite, although in small amounts. Applications: Ytterbium free from rare earths has very limited commercial applications. The element is used in lasers (102 nm) and as a doping agent. The radioisotope has been used in portable industrial units to examine thin layers of steel and aluminum sections and also in x-ray units for medical purposes. One of the most important uses of the element is in pure and applied experimental research. Ytterbium is mainly used in rare earths salt and metal mixtures. Mixtures of oxides containing ytterbium, are used in carbon bars for industrial lighting, in dielectrics and titanium capacitors and still as catalysts and addictive in glass production. The mixture of rare earth metals is used to control the grain size and to improve hardness and other mechanical properties of inox materials and non ferrous alloys. Biological Action: Most of the biological, biochemical, pharmaceutical and toxicological studies of ytterbium were performed in small animals, such as mice. The oral administration of ytterbium compounds has a very limited effect, once very little ytterbium is absorbed by the body. The subcutaneous injection provides a larger absorption, but the excretion of the element is rather slow. About 25% of the absorbed ytterbium is deposited in the liver and 65% in the bones, being the stockings lives respectively of about 15 days and 2,5 years. The rare earths, including ytterbium, have very little acute toxicity.
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71. Lutetium
History: Lutetium was first isolated in the oxide form, in 1907, by G. Urbain, that separated J. Marignac's yterbia in two distinct oxides which he called lutecia and neo-yterbia. The last is nowadays called yterbia. Almost simultaneously, A. Von Welsbach accomplished the same separation and baptized the two elements as cassiopeium and aldebaranium. In the middle of the 20th century lutetium was still referred in the German literature as cassiopeium. During that period, C. James, of New Hampshire, isolated the lutecia but it was the last of the three to publish its discoveries. The name lutetium derives of old Latin name of Paris, the native city of G. Urbain. Occurrence: Lutetium exists in low concentrations (from 0,05% to 1%) in many rare-earth minerals, such as xenotime, gadolinite, samarskite, fergusonite and euxenite. Most of the lutetium oxide is commercially obtained from monazite, where the concentration of the element does not surpass 0,003%. Usually, lutetium is obtained as a byproduct during the extraction of another rare earths as cerium and thorium. The largest monazite deposits are located in India, Brazil, Africa, Australia and USA. Biological Action: The lutetium salts are considered toxic since when inhaled or injected in large amounts cause serious disturbances. In spite of this, the investigators tend to classify the rare earths as having a relatively low toxicity.
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72. Hafnium
History: In 1911 Urbain and in 1922 Dauviller thought they had found a new element similar to the rare earths. Urbain called it celtium in honor of his country, France. In spite of this, the definite discovery and the determination of its properties and behavior was only accomplished in 1923 by Coster and Hevesy. The research of these scientists revealed amounts up to 30% of oxide of this new element in zirconium minerals. The discovery was made through spectroscopic techniques using zircon of Norway. Its X ray spectrum revealed the presence of the element 72, filling up the hole in the periodic table predicted by Bohr and Moseley. They named if hafnium after the Latin hafnia the word for Copenhagen. Occurrence: Hafnium is present in almost all the zirconium minerals, although in small quantities. Therefore, hafnium can not be considered a rare metal. Hafnium is extremely alike zirconium and can be isolated from this through a long process of fractional crystallization. Applications: The main use of hafnium metal is that of a control rod material for nuclear reactors, where its value is fully proved as a long-life high burn-up material. The high melting point and high electron emission of hafnium suggest uses in radio tubes, incandescent lamps and rectifiers and as cathode in x-ray tubes. The hafnium oxide is a refractory oxide with attractive properties whose high costs is the main drawback to wider usage as a high temperature material. Hafnium carbide, nitride and boride have some of the highest melting points known among compounds (3000 C to 4000 C) being the latter two highly conductive at high temperatures. Biological Action: There appears to be no evidence of any biochemical or biological activity of hafnium in living organisms. Further, the metal is nontoxic, as are its compounds, unless the latter hydrolyze to yield acidic solutions or vapors.
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73. Tantalum
History: In 1801, C. Hatchett found an unknown ore while he was analyzing some chromium minerals from Connecticut. He called "columbite" to the mineral, and "columbium" to the element, once it had been discovered from an American ore. One year later, in 1802, A. G. Ekeberg discovered a new element in Finnish minerals similar to "columbite" and gave it the name tantalum. This denomination derives from the Greek god Tantalus, as a reference to the enormous difficulty in dissolving the mineral in acids. In 1844, H. Rose found two new elements in a sample of "columbite" from Bodenmais. One of them was similar to the Ekeberg's tantalum. The other was called "niobium", in honor to Niobe, mythological daughter of Tantalus and goddess of the tears. The difference between tantalum and niobium was unequivocally made by Sainte-Claire Deville and by Troost, who determined the formulas of some of its compounds. The Hatchett's columbium was probably a mixture of these two elements, although the term has been used to refer to niobium. Occurrence: Tantalum does not occur free in Nature, but always associated to oxygen and other elements. The main tantalum ore is tantalite, being also possible to find this element in smaller amounts in samarskite, pyrochlore, fergusonite and euxenite. The main tantalite deposits are located in Africa (Rhodesia, Congo, Nigeria and Mozambique) and in Brazil. Also in Portugal and in Australia smaller deposits of this ore exist. Applications: The main applications of this metal are due to its inert chemical properties, resistance, hardness and ductility; thus, it is used in the production of chemical equipment with resistance to corrosion, or in high temperatures ovens, filaments for light bulbs, canalizations for switches of liquid metals in nuclear reactors, surgical instruments and implants, etc. The electrical properties of tantalum oxide made it useful in the production of rectifiers and capacitors. Tantalum carbide is used in the production of sharp instruments, with extreme mechanical resistance and hardness.
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74. Tungsten
History: In 1556, Agricola already referred to the existence of the mineral lupi spuma (the name means wolf's foam), today known as wolframite. It was so called due to the apparent tin "eating" during the extraction, like the wolf eats the sheep. The German name "wolfram" and symbol W are probably associated to this primordial denomination. In 1781, Scheele showed that the mineral known nowadays as scheelite, was a salt of calcium from a new acid, tungstic acid. In the same year, T. Bergmann recognized that the tungstenic acid was an oxide of a new element, which as called tungsten, from the Swedish expression to heavy stone. Metallic tungsten was produced for the first time in 1783 by J. J. and Elhuyar Don Fausto, two Spanish chemists that performed the reduction of the oxide with carbon. Occurrence: The more important tungsten ores are wolframite and scheelite; with smaller importance can also be considered tungstite and cuprotungstite. The largest world deposits occur in China (75% of the total), and in smaller amounts in other countries such as Portugal. The most important extraction mines in Portugal are located in Panasqueira and in Borralha, from which, during II World War, about 6000 tons of ores per year were extracted. Applications: Among its compounds can be stressed out the carbide (WC), representing about 40% of the world production of the metal. This compound is extremely hard and resistant, being used in the production of saw blades and other sharp utensils, abrasives, trunnions, ball-point pens, etc. The second largest application is in the production of special hard steels, with extreme resistance to corrosion and improved behavior at high temperatures. There happen to exist about 300 commercial ferrous alloys, with variable amounts of tungsten. It is also an important constituent of several non ferrous alloys, such as those formed with cobalt and chromium, with high hardness and resistance to abrasives, and still those formed with nickel, tantalum or niobium. All these alloys can be used in machinery pieces where high mechanical resistance is required. The most important applications of the pure metallic tungsten are the production of filaments for bulb lamps, electric contacts, arch-welding electrodes, heating elements in high temperature furnaces, valves for reaction propellers used in missiles and airships, etc. Among its compounds are the calcium and magnesium tungstates, used in fluorescent lamps, the disulfide used as lubricant at high temperatures and catalyst in the oil industry, the trioxide and the "tungsten bronzes" (by-products from the reduction of tungstates of alkaline and earth-alkaline metals), in the production of paints, etc.
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75. Rhenium
History: When Mendeleev compiled its first periodic table, left two vacancies in the manganese group, that constituted the only well-known element of this sub-group for a long time. The work of Moseley confirmed the existence of these two vacancies corresponding to the atomic numbers 43 and 75. One of these vacancies would only be filled in 1925 by W. Noddack, Ida Tacke and O. Berg, after the examination of the X-ray spectrum of certain platinum and niobium ores. They called this new element as "rhenium", from the Latin designation of Rhine (Rhenus). Four years after its discovery, 1 g of rhenium from 660 g of molybdenite was isolated. Shortly after its properties began to be carefully studied and its production began in Germany. Occurrence: Rhenium does not occur free in Nature, but is generally associated to molybdenites, MoS2 ores, that contain about 0,002 to 0,02% of this element. The molybdenites can be found in copper sulfide ores which represents an important commercial source of the element. Applications: The shortage and high cost of this element strongly limits its applications. However, due to its exceptional high temperature resistance and high melting point, rhenium is quite indispensable in the production of thermo-couples to measure temperatures up to 2500 C, in non-oxidizing atmospheres, as well as in the production of refractory alloys with tungsten, tantalum, niobium, molybdenum, etc. besides other smaller applications, it is used in powder as catalyst in hydrogenation and oxidation reactions.
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76. Osmium
History: Osmium was discovered, in 1802, by Smithson Tennant, while working in London. Tennant made a partnership with W. H. Wollaston, in 1800, with the purpose of developing and improving the platinum refining technology. One of the shipments of native platinum, from South America, was treated with aqua regia. The product, a dark residue, was melted with alkalis and treated with acid, distilled and then condensed, leading to a greasy liquid, with a strong and peculiar smell, and then to a semi-transparent solid. This solid was a compound of a new element, called osmium by those scientists. Its name derives from the Greek word for smell: osm. Occurrence: Osmium always occurs associated to other platinum metals, being however, the less abundant of these. The metals of this family occur mainly in Canada, in South Africa and in some countries of ex-USSR. From the Canadian deposits a mixture of ores is extracted that contain copper-nickel sulfides associated to volcanic rocks. The main deposits of South Africa are located in Merensky, northwest of Johannesburg. In Russia there are wide deposits of this metal in minerals like peridotite, in the area of Noril'sk, Siberia. Considerable deposits of native osmium in the Ural Mountains also can be met. Although in smaller amounts, platinum is extracted in Colombia and in Alaska. Applications: This metal, very hard and not very ductile, is mostly used in highly hard alloys for the production of pen nibs and pivots of several instruments. These alloys contain about 60% of osmium, some ruthenium and other metals of the platinum family. The tetroxide is used in organic chemistry as oxidizer and catalyst. Biological Action: The osmium tetroxide is extremely poisonous and lead to temporary blindness. Fortunately, its strong smell avoids extensive exposure.
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77. Iridium
History: Iridium was discovered and named by a British scientist, Smithson Tennant. About 1800 he began an extended association with W. H. Wollaston in London for the purpose of improving the technology of the fabrication of platinum. This metal had for some time been known to dissolve almost completely in aqua regia, but a small black residue always remained and was for a time thought to be graphite. In the summer of 1803 Tennant began a study of this material which ultimately resulted in the identification of both osmium and iridium Almost simultaneously in France, N. L. Vauquelin and A. F. de Fourcroy, in Paris were working on the black residue left after three successive extractions of native platinum with aqua regia and proposed the existence of a new element. These observations were complemented by H.V. Collet-Descotiles. There can be no question that Tennant's work owed much to the French research but he displayed greater insight than the latter. Iridium is a precious metal. It's the densest element known and has the highest corrosion resistance. Its mechanical is notable such as its elasticity (the second, after osmium). Iridium is hard, fragile and can be easily worked between 1200 C and 1500 C. Tennant chose the name iridium, from the Greek iris, rainbow, "from the striking variety of colors which it gives while dissolving in marine acid" Occurrence: Iridium always occurs associated with other metals from the platinum group. The major source are the nickel-copper ores of Canada, the pyroxinite deposits of the Transvaal, South Africa, and the extensive deposits of northern Siberia. There are also deposits in the region of the Urals. There are minor deposits in Colombia and Alaska. Applications: Iridium is normally used in the production of platinum alloys (with 5 to 10% of iridium) that makes the alloy harder and more resistant than pure platinum. The objects of platinum (medical equipment, jewelry etc) contain a small amount of iridium. The international metric standard is made of an alloy of platinum-iridium. The isotope with mass number 192 is used in industrial radiography.
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78. Platinum
History: The first reference to platinum appears in 1557 on the writings of Julius Caesar Scaliger as a description of a substance found in Central American mines ("up until now was impossible to melt by any of the Spanish arts"). In the middle of the 18th century there is a reference to platinum as a material that occurs mixed with gold in the mines of Colombia. The platinum name is a diminutive of silver (plata), due to the likeliness of their properties. During the 18th century the first platinum samples arrive to Europe, leading to the first metal experiences accomplished by the English physician William Brownring and communicated to the Royal Society, in 1750. In 1775, l'sle successfully melted platinum for the first time, after the separation from iron and sand. Pierre-Francois Chabaneau developed and patented, in 1786, a process to produce malleable platinum. The first sample of pure platinum seems to have been obtained in England, during 1803, by W. H. Wollaston while carefully studying several platinum solutions in aqua regia, what would also lead to the discovery of other elements such as palladium or rhodium. The method used by Wollaston was a predecessor of the modern metallurgical techniques to produce platinum. Occurrence: Platinum mainly occurs in Canada, in South Africa and in some countries of the former-USSR. From the Canadian deposits a mixture of ores is extracted that contain coppernickel sulfides associated to volcanic rocks. Platinum and palladium can be found in this minerals in equal amounts while the presence of silver or gold is residual. The main deposits of South Africa are located in Merensky, northwest of Johannesburg. Here the platinum occurs in the order of 4 to 10 ppm, in rocks as piroxene, but always associated to iron, copper or nickel chromides and sulfides. In Russia there are wide deposits of this metal in minerals like peridotite, in the area of Noril'sk, Siberia. Can also be met considerable deposits of native platinum in the Ural Mountains. Although in smaller amounts, platinum is extracted in Colombia and in Alaska. The abundance of platinum in the earth crust is of the order of 0,01 gram per ton (i.e., about the double of that of gold). Applications: Platinum is mainly used in the free metal form, as catalyst in hydrogenation reactions performed in organic chemistry. It is also used in the preparation of gasoline to increase its yield and in the purification of gases for catalytic oxidation. Metallic screens made of platinum-rhodium can be used to catalyze the ammonia oxidation in nitric oxide to prepare nitric acid. Pure platinum is used, in resistive thermometers and in thermo-couples, with a platinum-rhodium alloy. This alloy is used during the process of producting artificial silk and glass fibers. The alloy of platinum-iridium is used in jewelry, laboratory utensils, electrodes and electric contacts. Alloyed with palladium, platinum is used in dental prosthesis.
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79. Gold
History: It is probably the first metal discovered by man. Gold and the search for it have been among the major factors in exploration, conquest, and growth of civilization. Archaeological studies have shown that the goldsmiths art dates from at least 4000 B.C in Mesopotamia and that it then spread troughtout the whole group of ancient civilizations around the eastern Mediterranean, including Egypt. It also arose in the New World in the PreColumbian cultures of Peru and Mexico, as well as in the Asian civilizations. The earliest written records of all nations mention gold and its uses and value More recently, alchemy, based on the search for the Philosophers Stone which would convert base metals to gold, contributed to chemistry, medicine and metallurgy. Occurrence: Gold is widely distributed throughout the world, normally in very low concentration and generally in native form as metal. It is usually alloyed with silver and often contains small amounts of copper. The only compounds of gold found in nature are the tellurides, typically calaverite (AuTe2), petzite ((AuAg)2Te), sylvanite ((AuAg)Te2), among others. Gold is found in native form in both lode and alluvial deposits. In the largest gold reefs of the world, in South Africa, gold is present as veins and stringers in a quartz matrix accompanied with pyrite and quartz sand. Many pyrite and pyrhotite minerals contain gold from which the metal is recovered during the extraction of copper, silver, lead, zinc and nickel. Although in low concentrations, gold is also present in the sea water, being conservatively estimated that the oceans contain 70 million tons of gold in solution. The major world producers of gold are South Africa, the countries of the old USSR, Canada, the United States and Australia. Uses: One property of gold that distinguishes is from all other metals is its universal status as a monetary standard. Gold has been used as a medium of exchange since 3000 B.C. In the late 1700s it became the world monetary standard. Most of the world production is absorbed by governments. Some metal is used in coinage, but the chief use is for backing currency and to settle international trade balances. Probably over one-half of the total world production is in government vaults or central banks. The major non-monetary uses are both decorative and functional. The decorative uses include jewelry, religious items, etc. Functional applications occur in electronic and space industry. It is usual to make electrodepositions of gold on electronic components, including heat shields, diodes, printed circuits, tube pins and plugs. Thin gold films are excellent infrared reflectors with corrosion resistance and low contact noise. Other functional applications include dental alloys, electrical contacts, chemical equipment, photography, etc Biological Action: Gold is used in the treatment of arthritis, generally being administered intramuscularly. Colloidal suspensions of radioactive Au198 have been used in treating several forms of cancer.
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80. Mercury
History: Mercury is often found in the native form, and sometimes in very odd places. The metal had been found in some mountain Spanish regions, in wells. Mercury was already known in the Antiquity by Chinese and in India. We can also find mercury in Egyptian graves that date of middles of the second millenium before Christ. The investigators think that the only wellknown mercury ore in Antiquity was the cinnabar. Teofrastus (300 B.C.) described the method used to extract mercury from cinnabar, through the interaction of the metal with cooper and vinegar. Aristotle used to call mercury, the liquid silver and Dioscoride knew this element as water of silver, in Latin hydrargyrus. Occurrence: Native mercury is extracted in mines all over the world. The biggest mercury producers are Spain (Ciudad Real) and Italy (Trieste), followed by the USA, Mexico, formerUSSR, China, Japan, etc. Uses: The major applications of mercury are in electrical equipment and in control devices, where the fluidity stability, high density and electrical conductivity are essential. This metal is also used in the agriculture (as fungicide and bactericide), in dental preparations, in the electrolytic preparation of chlorine and alkalis, in pharmaceuticals, etc. The mercury compounds have more limited applications than the metal. The mercurous chloride (calomel) is one of the oldest known pharmaceuticals; it is still used as antiseptic. The red mercury oxide is used in mercury batteries, developed during II World War, which are compact and stable energy sources. The mercuric chloride prevents attacks of fungus in seeds, bulbs and it is good to amalgamate aluminum, zinc and other metals. The organic compounds that contain mercury are commercially important as microbial agents. Biological-Toxicological Nature: The main route of mercury absorption is via the respiratory tract. In spite of this, mercury can also be absorbed when in contact with the skin and through the gastrointestinal tract. The toxic signs of mercury illness are readily recognized. Vapor inhalation chronic toxicity is marked by sore throat, listlessness, tremors abdominal discomfort and other signs. Other chronic disease indications are nervousness, irritability and other personality changes. Personnel exposed to mercury and its compounds should employ protective equipment such as impermeable gloves and eye protection.
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81. Thallium
History: Thallium was discovered in 1861 by Sir William Crookes, through spectroscopic techniques, during his seek for tellurium, in some plant residues. Crookes found a sharp and unknown green stripe in the spectrum of some acids removed from those plants, and proposed the existence of a new element. This green stripe reminded Crookes, the color of the vegetation in Spring. For that reason, he called it thallium, that derives from the Latin word thallus, which means "in bloom". During that year, Crookes isolated a small amount of metallic thallium, and exhibited it at an international conference in London, in 1862. The French professor Lamy was also well successful in identifying this new element by the spectroscopic techniques of Crookes. At first, thallium was thought to be an element from the sulfur family. However, this erroneous idea was quickly abandoned since it possessed properties similar to those of lead, mercury and aluminum, its correct position being attributed in the periodic table in group IIIA. Occurrence: The abundance of thallium in the Earth crust is about 1 gram per ton. It is interesting to notice that, according to this estimation, thallium is more abundant than other well-known metals, such as mercury, antimony, bismuth, cadmium and silver. The element is widely spread throughout the earth crust but its direct extraction is very expensive and ineffective. Thallium usually occurs associated with potassium minerals and is extracted as a byproduct. Applications: Thallium and its compounds have very little applications, being normally limited to commercial insecticides and rat poison. Thallium sulfate is an insipid and scentless compound, and is usually added to glycerin, sugar or water to eliminate small rodents and bugs. Thallium applications as a metallic alloy are also limited. The only important alloy is thallium-lead that is used in electric fuses. Thallium is also used as an addictive in special glasses, used in semiconductor protection, capacitors and other electronic devices, to protect them from oxidation and moisture. Biological Action: The handling of thallium should be made with extreme care to avoid its toxic effects. In contact with air or water, the metal quickly forms soluble compounds, normally considered toxic. Thallium poisoning syntoms are quick hair loss and internal functional disorders.
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82. Lead
History: Lead was probably one of the first metals to be produced by man, being known since 3500 B.C., in agreement with archaeological discoveries done in Egypt. The oldest lead piece is in the British Museum and dates from 3800 A.D.. The manner in which prehistoric people extracted lead from its minerals is not wellknown. However, there are vestiges of very rudimentary furnaces, done of stone, where these people heated up the lead minerals with bonfires (that burned wood and coal) to extract the element. There is also evidence that the Chinese already produced metallic lead about 3000 B.C., and that Phoenicians had explorations close to deposits in Spain, in 2000 A.C.. In the 5th century B.C. the Romans made an extensive exploration of lead deposits in the whole Iberian Peninsula. In the period 700 A.D. to 1000 A.D. the German mines of lead and silver, in the Rhine valley and in the Hartz mountains, were very important, just as those of Saxony, Silesia and Bohemia in the 13th century. In the 17th century, the lead foundries flourished in Great-Britain, specially those located in Wales and Derbyshire. Occurrence: Lead is not very abundant, its relative rates being smaller than those of other metals as the aluminum, iron, magnesium, titanium, nickel, etc.. However, it is more abundant than cobalt, tin, cadmium or gold. The more important lead minerals are galena (PbS), anglesite (PbSO4) and cerussite (PbCO3), respectively with 86%, 68% and 77% of lead. Other minerals that contain lead are linarite, pyromorphite, mimetite, vanadinite, crocoisoite and wulfenite. The main deposits of lead minerals are located in the USA, Peru, Argentina, Bolivia, Australia, Zambia, South Africa, Germany, Spain, Sweden, Italy and Serbia. Applications: Lead is one of the most used metals in industry, being just surpassed by other metals as iron, copper, zinc and aluminum. The main application of lead and of its oxide (PbO) is producing electrical batteries for vehicles. Lead alloys are largely used in industry. The addition of a small percentage of arsenic, or antimony, to the lead, increases its hardness and mechanical resistance, protecting it from abrasion. The calcium-lead and the tin-lead alloys are used in coating certain electrical cables. Current solder is a lead-tin alloy, in variable proportions in agreement with the requested melting point. The bismuth, cadmium or mercury addition can also affect the melting point of solder. Biological Action: Generally, lead compounds are noxious for the animals. The effect of the absorption of the element in plants does not seem serious. However, this accumulate lead will be absorbed by the animals in case of ingestion. That is why lead compounds are not used in pesticides or insecticides. Lead and its sulfide are incapable of absorption, and are considered practically innocuous. However, the soluble salts, such as the chloride, the nitrate, the acetate, etc. are very poisonous. The main intoxication cause with lead is the exposure to vapors and dusts of its compounds. The intoxication symptoms are intestinal mal-function, strong abdominal pains, diarrhea, appetite loss, nausea, vomiting and cramps.
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83. Bismuth
History: Bismuth was probably not recognized as a specific metal by the early Orientals, Greeks or Romans, but by the Middle Ages, Europeans were becoming aware of its specific nature, and in the 15th Century Basil Valentine referred to it as wismut. The early mineralogist Georgus Agricola, at the end of the 16th Century, latinized wismuth to bisemutum. Only in the middle of the 18th Century, through the research of J. Pott, C. Geoffroy and T. Bergma, was bismuth definitely recognized as a specific metal. Occurrence: The abundance of bismuth in the Earths crust has been estimated to be 0.000002 %, about the same order as silver, less than tin, but more than gold. Bismuth occurs both as native bismuth and in ores. The native bismuth is not abundant but is found in veins associated with silver, lead zinc, and tin ores in places such as Saxony, Bolivia, Canada and England. The most important ores are bismite, or bismuth ocher (Bi2O3), bismuthinite (Bi2S3) and bismutosphaerite (carbonates). Applications: Bismuth is used in pharmaceutical industry, in the production of cosmetics and in the chemical and metallurgical industries. The pharmaceutical uses are principally in ingestion remedies. Soon after the discovery of bismuth as a distinct metal in the 15th Century, various of its compounds were recommended for a wide variety of diseases. By the latter 18th Century bismuth compounds were used with remarkable success in treating gastric spasms and dyspepsia. After World War I, the value of bismuth chemotherapeutic in the treatment of syphilis was recognized. In the cosmetics industry, bismuth oxychloride is used to produce such products as lipsticks, eye shadow, etc. In the chemical industry, bismuth is used in the manufacture of plastics, in the synthesis of methanol and as a catalyst. It is also used in the production of low melting alloys used in protective coatings for wood patterns and other metals, as fuses and in short life dies. Intermetallic compounds of bismuth with tellurium or selenium are used in thermoelectric materials for making use of the Peltier effect for refrigeration, used in semiconductor devices such as CCDs or photodiodes. Bismuth is also used in the production of permanent magnets. Biological Action: Toxicity is not a problem in handling bismuth. It is one of the least toxic of the heavy metals, and cases of bismuth poisoning in industrial use have not been reported.
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84. Polonium
History: Polonium was discovered in 1898 by Pierre and Marie Curie, who named it in honor to Poland, the native country of Marie Curie. It was the first element to be discovered through its radioactivity, and at the time its discovery was quite doubtful. In the first attempt to isolate polonium, Marie Curie treated almost a ton of uraninite to obtain a small amount of a material with a radioactivity 400 times superior to that of uranium. Marckwald noticed that this material had identical chemical behavior to tellurium, suggesting the name radiotellurium. In the same year of 1898, Marie and Pierre Curie identified another element, radium. In the following years, chemists and physicists studied of the decay tree of radium, and concluded that polonium was the last member of that decay. The atomic mass of polonium was derived from Marie Curie's calculations of the atomic mass of radium. Polonium was undoubtfully recognized as an element in 1905, when it received its definitive place in the periodic table, in the selenium and tellurium group. Occurrence: Polonium does not have any stable isotopes and it is one of the scarcest elements than occur in Nature (in uraninite and other uranium ores). Applications: The study of polonium compounds is particularly difficult due to the high radioactivity of the element, limiting the working amounts. Although limited, polonium applications are restricted to certain laboratories, and mainly as alfa particle and neutron sources. Biological Action: The toxicity of polonium is almost exclusively due to its isotope Po 210, which has high radioactivity. When ingested, polonium tends to concentrate in the kidneys, the spleen and the liver, causing irreversible damage due to the emission of alpha particles.
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85. Astatine
History: During the 1920s and 1930s several workers claimed to have found element 85 in natural sources. We know today, however, that all astatine isotopes are highly radioactive, and the amount of astatine present in nature is so small that these early reports must be erroneous. The element was first characterized in 1940 by Corson, Mackenzie and Segr, who synthesized the isotope At 211 by bombarding bismuth with alpha particles. They observed chemical behavior somewhat similar to that of other halogens and named the new element astatine, from the Greek astatos, meaning unstable. Biological Action: When injected as a mononegative ion into experimental animals, astatine concentrates in the thyroid. The alpha-emitting astatine isotopes offer an advantage over radioiodine in the treatment of hyperthyroidism and thyroid cancer, since the alpha deposit more energy in a limited area than the beta particles of the radioiodine. However, astatine has shown a tendency to induce tumors and this obviously presents a severe obstacle to its clinical use.
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86. Radon
History: In 1899, R. B. Ownes noticed that the radioactivity of the thorium compounds tended to dim when exposed to the air. Rutherford studied this effect, and discovered that the thorium emitted a radioactive gas, well-known at time as "thorium emanation". In 1900, F. E. Dorn verified that the same effect occurred with radium, and in 1903, A. Debierne and F. O. Giesel recognized the same "emanations" in actinium. The likeness of the spectra of these gases with those of argon, krypton and xenon, and the its chemical inertia suggested that the "emanations" could contain a new element from the noble gases family. This element was finally baptized as radon, in 1923. Occurrence: The radon atom is highly unstable. All its isotope have extremely short half-lives and emit alpha particles, becoming polonium. Radon is formed during the disintegration of radium and, therefore, all the minerals that contain radium should also contain radon. Applications: Radon has been used as a radiation source in cancer therapy, with some advantages over radium. It is also used as radioactive tracer to spot gas leeks and in fluid measurements. Biological Action: Long exposure to high doses of radon can induce lung cancer as well as red cell decrease. This is a problem especially to uranium mines workers.
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87. Francium
History: Francium was discovered in 1939 by the Frenchwoman Marguerite Perey, who established the presence of a 21-minute radio-isotope with properties of an heavy alkali element among the decay products of actinium. Mlle. Perey also isolated this product, determined its radio-chemical and nuclear properties, and showed that actinium is a product of radioactive decay. The initial proposed name was "actinium K", following the naming system for natural radioactive sources. Later, she proposed the name francium in honor of her country - France. With the exception of some transuranians, francium is the most unstable element known. Its chemistry is not well known but we can say that it is similar to the other heavier elements of the family such as rubidium and cesium. Occurrence: Francium occurs in very low concentrations in uranium ores as the result of the alpha decay of actinium. It can also be synthesized by bombarding thorium with protons. There are at least 19 francium isotopes and the longest one (223) has a period of 21 minutes.
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88. Radium
History: In 26th December 1948, Pierre and Marie Curie announced the discovery of this element. It had been distinguished from polonium due to the likeliness of its chemical properties with those of barium. Its sulfate and carbonate were insoluble and the chloride was soluble in water but insoluble in hydrochloride acid or in alcohol. However, this element was not identical to barium, and could easily be separated. The existence of a second element, demonstrated by its radioactive properties, was confirmed by a foggy line in the spectrum of barium. This new element was called "radium". Some years later, in 1902, Madame Curie performed a series of fractional crystallizations starting from a considerable amount of uraninite residues, and was able to isolate about 0,1 grams of chloride of almost pure radium, with an activity about 3 million greater than that of uranium. The announcement of the discovery of polonium and of radium triggered a series of research works, leading to the discovery of another radioactive elements associated to uranium and thorium. Occurrence: Radium occurs in all uranium ores, and is produced by radioactive decay. Due to the high solubility of its compounds in water, radium is extracted by successive lixiviation of the referred ores. Uraninite contains about 300 milligrams of radium per ton of uranium, but, in spite of this, the amount of radium in earth crust is estimated to be about 18 million tons. Applications: Radium and its compounds had been industrially used since the first half of the century, in the production of glowing paints. These paints glow due to the presence of inorganic phosphorus compounds, excited by alpha particles emitted by radium. The required small amount of radium is extracted from uraninite, a uranium ore with radium residues. Radium can also be used as neutron emitter in nuclear reactions. Can also be used in radiotherapy, due to the intense emission of gamma rays of daughter nuclei. Radium is an important source of radon, the heaviest rare gas. Biological Action: Radium is extremely toxic due to its radioactivity. The maximum admissible amount of radium in the human body is about 0.1 micrograms Due to the likeness of its chemical properties with those of calcium, radium tends to accumulate in the bones and interfere with the blood red cell formation process in the bone marrow. In extreme cases can lead to bone cancer.
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89. Actinium
History: Actinium was discovered by Debierne in 1899 and independently by Gisel in 1902, in the rare earth fraction of pitchblende residues. The name actinium (aktis, ray) was proposed by Debierne. The genetic relationships of the members of the actinium decay series were determined during the next twenty years by radiochemical studies. The parent of the series, U235, and the mass numbers of all its members were established by Dempster in 1935, by mass spectrometric analysis. Occurrence: Actinium-277 occurs in small amounts in all uranium ores. Two other isotopes of actinium are also found in trace amounts in Nature, Ac228 and Ac225. Eight additional isotopes of actinium have been produced artificially by nuclear reactions. Physiological Behavior: Although actinium is primarily a beta-emitter, it should be classed as a hazardous radioactive poison of high specific alpha-activity along with radium and the transuranium elements plutonium, americium and curium. In the human body, actinium has tendency to accumulate and to be tenaciously retained by the skeleton, in the superficial layers of the bone structure. The elimination rate of actinium from the body is much less than the rate of radioactive decay.
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90. Thorium
History: In 1815, the Swedish chemist J. J. Berzelius obtained a material which he regarded as a new earth. He assigned this to a new oxide and the corresponding metal name was intended to honor Thor, the ancient Scandinavian god of thunder. However, in 1824, he demonstrated that this supposedly new earth was essentially the phosphate of previously discovered yttrium. Four years later, the Reverend H. M. T. Esmark discovered a black mineral on the island of Lovo near Brevig, Norway; he gave a sample of this material to his father, Professor Jens Esmark, a noted mineralogist. Professor Esmark was unable to identify it as any known mineral, so he in turn sent a specimen to Berzelius for examination. A chemical analysis of this mineral by Berzelius demonstrated that it contained almost 60% of a new earth which he reported as distinct from all others known. It appears that, in naming this new oxide "thoria" and the mineral which it was obtained "thorite", Berzelius fully restores the dignity of Thor from the earlier near humiliation. The discovery of thorium was announced by Berzelius in a publication in 1829. He also prepared thorium in metallic form in that year by heating a mixture of potassium metal with potassium thorium fluoride in a glass tube. The metal appeared as a gray powder since the reduction reaction was not sufficiently exothermic to melt the thorium metal product. Thorium and its compounds were used only for academic purposes until 1884, when Auer von Welsbach developed and patented the incandescent gas light mantle in which thorium oxide was the essential ingredient. The mantle industry grew to its peak in the early of the 20th century, but as electricity began to replace gas for general lighting purposes, mantle production decreased and by 1925 thorium was relatively unimportant to commerce. With the advent of atomic energy, thorium jumped back to an important role in nuclear power plants due to its nuclear properties. Occurrence: Thorium, which makes up about 0.0015% of the earth's crust, occurs in a large number of minerals in association with the rare earths and uranium. The major source of thorium is monazite (a phosphate of the light-weight rare earths) usually associated to silica. The main deposits of monazite are located in India, Brazil, Australia, Malagasy, Ceylon, South Africa, Canada and U.S.A. From all these the most important is that of India, with huge deposits of ore with a concentration that averages about 9% of thorium oxide. Applications: The most important application of thorium is the production of nuclear power either as metal, oxide or alloy and even in several compounds during the U 233 production process. In the non-energetic uses, the production of gas light mantle and the use of thorium metal for imparting strength to magnesium metal can be included. Due to its low work function and high electron emissivity, has found applications in a number of gaseous discharge lamps, photoelectric cells (when ultraviolet sensitivity is required) and as emitter in monochromatic Xray tubes. The oxide has been found useful in a variety of areas. Perhaps the most recent potentially large-scale nonenergy use found for thorium oxide is as hardener of nickel for space and metallurgical industry. Thorium oxide, when properly prepared, is quite active as a catalyst for many chemical processes, like oil fractionizing and sulfuric acid preparation. Its stability at high temperatures allow the use as a coating element for melting crucibles. Biological Action: Hazards of thorium or its compounds may generally be classed into three types, namely, radiological, chemical and combustion. The radiological hazards of thorium are connected essentially with the radioactivity of the isotopes in the decay chain from thorium-232 to lead-208. In the body the thorium-type isotopes generally tend to concentrate in the liver, kidneys, spleen and bone marrow. Ordinary chemical toxicity of thorium or its compounds by means of introduction into the body is generally considered low. However, intravenous injections of thorium compounds, on the other hand, are more toxic leading to serious perturbations or even death. Some alloys of thorium pyrophoric and may, even in massive form, ignite or rapidly disintegrate on exposure to air. The greatest danger of fire and explosion from the metal and
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alloys is when they are in powder form. For all these reasons, thorium and its alloys should be handled with extreme care and with adequate utensils and cloathing.
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91. Protactinium
History: The first isotope of protactinium to be discovered was Pa 234m (also called UX2), an ephemerous member of the natural decay series of U 238. This isotope was identified by Fajans and Gohring in 1913, who called it brevium at the time. Almost simultaneously, in 1918, two research scientist teams isolated a more stable isotope (Pa 231), of the decay series of U 235. These teams were led by Hahn and Meitner, and by Soddy and Cranston. Initially christened protoactinium, the element saw its name being contracted for protactinium. Occurrence: Due to the small half-life of the isotope Pa 234, its natural abundance is very reduced; however, the stable isotope (Pa 231) has an abundance comparable to that of radio. Thus, in the uranium ores, for each ton of natural uranium there are 340 mg of Pa 231 in radioactive balance. Biological action: The isotope Pa 231 is a vigorous alpha particle emitter and therefore a dangerously toxicant material. Its handling requests the same care as Pu 239.
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92. Uranium
History: Pitchblende was thought to be a ore with zinc, iron and tungsten. However, in 1789, the German chemist M. S. Klaproth discovered a new element in pitchblende ores which he named uranium in honor of the planet Uranus, which had been discovered just eight years before. The French scientist Henri Becquerel discovered the radioactive property of uranium in 1896. Enrico Fermi and his coworkers observed in 1934 that the bombardment of uranium by neutrons produced beta radioactivity, although the full significance of this observation was not understood at the time. In 1938, Otto Hahn and Fritz Strassmann showed that when uranium was bombarded by thermal neutrons it fissioned into radioactive isotopes of lighter elements, such as krypton and barium, and that part of the binding energy holding the protons and neutrons together in the heavy uranium nucleus was released. In 1939, at a conference in the United States, Fermi suggested that when uranium nuclei are split under neutron bombardment other neutrons might also be released in sufficient number to cause a continuous self-sustaining fission reaction. The existence of these fission neutrons was confirmed in 1939 in studies by F. Joliot, Leo Szilard, H.L. Anderson and their coworkers. The first self-sustaining nuclear chain reaction was achieved by Fermi and a team of scientists in a pile of 400 tons of graphite, six tons of uranium metal and 58 tons of uranium oxide, at the University of Chicago, on December 2, 1942. The first test of a nuclear explosive device occurred on Alamogordo, New Mexico, on July 16, 1945 and the first nuclear weapon was used in warfare August 6, 1945, at Hiroshima. Occurrence: Uranium is found to some extent in the majority of rocks and sediments making up the Earth's crust, but is never found in concentrated deposits. The most common uranium ore is pitchblende, which consists of a mixture of UO2 with U3O8. The largest known source of pitchblende is located in the Leopolville mines, in Congo, Africa. Other uranium containing minerals are euxenite, carnotite, brannerite and coffinite. The largest deposits of these ores are located in the USA, Canada, Russia and France. Applications: Before the advent of the nuclear energy, uranium had very limited uses. It was only used in filaments for lamps. Compounds of uranium have been used in photography for toning, and in the leather and wood industries for stains and dyes. Uranium salts are mordants of silk or wool. By far the most important use of uranium lies in its application for nuclear (or atomic) energy. Three isotopes of uranium are of prime importance to the development of nuclear fuels and explosives (U 233, U 235 and U 238), being the most important U 235. For producing nuclear energy, there is a self-sustaining reaction, which occurs in a reactor, usually immersed in a cooling and moderating substance - water. Water is heated up and vaporized, powering up turbines which act on generators to produce electrical energy. Nuclear reactors can be quite compact, being normally used for marine propulsion in submarines and warships and in space probes like those of Voyager and Pioneer. Biological Action: Uranium has important applications in medicine. Its isotopes are used in diagnostics and therapy of various illnesses.
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93. Neptunium
History: Neptunium, whose name derives from the planet Neptune, was the first synthetic transuranian element to be discovered. Its isotope, Np 239, was produced by McMillan and Abelson in 1940, in Berkeley (University of California), as by-product of the bombardment of uranium with cyclotron neutrons. These investigators suspected that Np 239 should decay to another element with higher atomic number. This fact was confirmed with the discovery of the plutonium by Seaborg, McMillan, Kennedy and Wahl, in 1940. The Np 237 isotope is obtained, in the order of kilograms, as by-product in nuclear reactors. L. B. Magnusson and T. J. LaChapelle obtained this isotope in measurable amounts for the first time in October of 1944, in the Metallurgy Laboratory of the University of Chicago, as product of beta decay of U 237. Occurrence: It is possible to find residual neptunium in Nature due to transmutation reactions in uranium ores, produced by neutrons of natural sources.
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94. Plutonium
History: Plutonium, whose name derives of the planet Pluto, was the second transuranian element to be discovered; isotope Pu 238 was produced, in 1940, by Seaborg, McMillan, Kennedy and Wahl, in the University of California - Berkeley, through the bombardment of uranium with deuterons, in a 60 inches cyclotron. The most important of its isotopes is Pu 239, produced in great amounts in nuclear reactions as a uranium by-product. In August 1942, B.B. Cunningham and L.B. Werner succeeded to isolate about a microgram of Pu 239, in the Metallurgical Laboratory of the University of Chicago. This made plutonium the first synthetic element to be obtained in visible amounts. Those scientists isolated a sample of 2,77 micrograms, in September 10 of that year. Applications: Plutonium has been taking a prominence position among the transuranians, due to its fruitful usage in nuclear weapons, as well as in the development of the nuclear energy industry; about 1/4 Kg of plutonium produces ten million kilowatt-hour of heat. Its importance derives essentially from its fission readiness by neutrons. It is possible to observe plutonium in natural uranium ores, although in residual amounts. Its formation process is very similar to that of neptunium, resulting from the irradiation, with neutrons, of natural uranium. Biological Action: Due to its high rate of alpha particle emission, and to the physiologic particularity of the element absorption by the bony medulla, plutonium is radiologically poisonous (more than any other transuranian). It must therefore be handled with extreme care and special equipment.
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95. Americium
History: Americium was prepared for the first time in 1944/45, by Seaborg, James, Morgan and Ghiorso, through the neutron irradiation of plutonium samples. These researchers discovered the elements 95 and 96 while plutonium was being produced in industrial proportions, in Hanford, to be used in nuclear weapons. Their labor lasted more than one year, being the difficulties so big that one of them suggested that the newly found elements should be called pandemonium and delirium. In spite of this, the elements were given the names americium (in analogy with europium) and curium, honoring Marie and Pierre Curie. This discovery was announced in a very peculiar way. When asked by students, in a radio show, in November 1945, Seaborg pointed out that during the war, research and development in nuclear weapons had took place, leading to the discovery of two new elements. Nowadays we know that this was the truth, but it was difficult to the youngsters who ran the radio station to convince their teachers that Seaborg was not joking. Occurrence: Americium is the third artificial element heavier than uranium, the preceding ones being neptunium and plutonium. Since americium is relatively short-lived and has no long-lived precursor, is not found as a naturally occurring element. It is made in nuclear reactors by multiple neutron capture in plutonium. Uses: The isotope 241 has been used as a portable source for gamma radiography, taking advantage of the 59 keV gamma that accompanies the majority of the alpha emission. The heavier isotope Am-241 is being used for chemical studies and as a source of Cm 244, which is being made in kilogram quantities as an isotopic power source.
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96. Curium
History: In the Summer of 1944 G.T. Seaborg, R. A. James and A. Ghiorso, working at the Manhattan Project, performed a careful chemical fractionation on a sample of plutonium which had been irradiated with 32 MeV helium ions at the University of California. A new radioactive isotope was found, which emitted 4.7 MeV alpha particles and was chemically separable from neptunium and plutonium. Both nuclear and chemical evidence indicated that the activity could be ascribed to an isotope of a new element with atomic number 96. In tribute to the brilliant pioneering achievements of Pierre and Marie Curie in the field of radioactivity the new element was given the name curium. Visible amounts of curium were not isolated until 1947, when L.B. Werner and I. Perlman, working at the University of California's Radiation Laboratory in Berkeley, obtained about 30 micrograms of the curium isotope of mass 242 as pure hydroxide. The crystal structure and melting point of curium metal were determined in 1964 by B.B. Cunningham and J.C. Wallmann. Applications: Both Cm 242 and Cm 244 are used in the thermoelectric generation of power for the operation of instruments at remote terrestrial locations or in space vehicles. A power package utilizing the isotope of mass 244 can maintain a nearly constant output for many years. Biological Action: Curium absorved into the body tends to accumulate in the bones. The shorter-lived isotopes are extremely toxic due principally to the radioactive destruction of the red cell forming mechanism. The maximum permissible human body burden of Cm 244 is 0.002 micrograms.
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97. Berkelium
History: In December 1949, S.G. Thompson, A. Ghiorso and G.T. Seaborg carried out an ionexchange separation of the products formed by the irradiation of milligram quantities of Am 241 with 35 MeV helium ions. A 4.5 - hour electron-capture activity eluting just ahead of curium was assigned to an isotope of a new element with atomic number 97 and mass number 243. The new element was named berkelium for the city of Berkeley, California, where it was discovered. A visible amount of berkelium was isolated for the first time by Thompson and Cunningham at the University of California Radiation Laboratory in Berkeley in 1958. The first determination of the structure of a berkelium compound was carried out by Cunningham and J. C. Wallmann in 1962, using X-ray diffraction methods. The metal can be made by reduction of BkF3 or BkF4 with calcium. Occurrence: Berkelium does not occur naturally. The element is made by nuclear synthesis. The lighter isotopes are made by charged particle bombardment and the heavier ones by neutron irradiation of large quantities of plutonium, americium or curium. Applications and Biological Action: Berkelium has no technological uses at present and its limited availability has precluded an extensive investigation of its properties. It has been shown in experiments with rats and mice that actinide elements taken into the body tend to accumulate in the skelet. The radiations associated with these isotopes damage the body red-cell forming mechanism. The toxicity of the individual isotopes varies, depending on the type of radioactivity and half-life. The maximum permissible burden of Bk 249 in the human skeleton is about 0,0004 micrograms.
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98. Californium
History: On February 9, 1950, S. G. Thompson, A. Ghiorso, K. Street and G. T. Seaborg performed a careful ion exchange separation of the products formed by irradiation of microgram amounts of Cm 242 with 35 MeV helium ions produced by the 60-inch cyclotron at the University of California, Berkeley. A new radioactive isotope was found, which eluted just ahead of berkelium, in the position expected for element 98. This activity, was assigned to an isotope with mass number 245. The new element was named californium for the state in which it was discovered. A sufficient amount of californium had to become available to carry out the first experiment with the pure element in concentrated form. B. B. Cunnigham and Thompson, working at the University of California's Radiation Laboratory in Berkeley, concentrated about 0,1 micrograms of californium for a measurement of the magnetic susceptibility. In 1962, J. C. Wallman and Cunningham, determined the crystal structures of two californium compounds. Occurrence: Since there are no natural sources of californium, the element must be prepared by nuclear synthesis; the known isotopes may be obtained by charged particle bombardments, the heavier ones by neutron irradiation. It is also possible to find compounds among the byproducts of thermonuclear explosions. No matter the process used to obtain californium, this element represents always a small fraction of the reaction byproducts. Usually fractionizing techniques are required to separate the element. Applications and Biological Action: The decay of Cf 252 by spontaneous fission makes the isotope a convenient highly portable neutron source of neutrons. Cf 252 could be used for radiographic purposes or as a source of neutron for neutron activation analysis of planetary surfaces or for logging in deep drilling operations. Similarly to other actinide elements, californium tends to accumulate in the skelet, where it damages the red cell forming mechanism. The maximum permissible burden of Cf 252 in human body is 0.00006 micrograms (or 0.009 micrograms in the case of Cf 249).
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99. Einsteinium
Einsteinium is the seventh of the man-made transuranium elements and the tenth member of the actinide series. Since elements 99, einsteinium, and 100, fermium, were found at the same time, their discoveries will be described together. History: During 1949, the preceding two elements, berkelium (97) and californium (98) were synthesized in minute amounts. It was then clear that the synthesis of elements beyond californium could be achieved by two methods: exposing heavy elements to a very high neutron flux, or bombarding them with heavier ions, such as carbon or nitrogen. The Materials Testing Reactor in Idaho came into operation during 1952, and provided a neutron flux an order of magnitude higher than previously available. At the same time, techniques for accelerating useful beams of heavy ions were being developed in several laboratories. These developments ensured the eventual synthesis of elements 99 and 100, but the first observation of these elements came unexpectedly, from a quite unrelated experiment - the explosion of the first thermonuclear bomb in the Pacific during November 1952. Samples of debris were collected by drone aircraft flying through the cloud and analyzed. Among the new activities detected were alpha-emitters of 6.6 and 7.1 MeV, indicating that a brief exposition to a very high neutron flux can have similar results to the slow irradiation by heavy elements made on the labs in Idaho. From the analysis of these samples it was possible to identify the source of the alpha particles with that specific energy as the new elements 99 and 100 respectively. For security reasons, these observations in late 1952 and early 1953 could not be published in the open literature. The first publication concerning element 99, in 1954, reported the production of a 7.3 minute isotope. Shortly afterwards, also in 1954, the detection of elements 99 and 100 in plutonium samples which had been exposed to an intense neutron flux was reported. The full story of the discovery of elements 99 and 100 was finally published in mid-1955 by a group of authors of the laboratories involved. Element 99 was named einsteinium, in honor of Albert Einstein, and element 100 was named fermium, in honor of Enrico Fermi. Occurrence: Einsteinium is an artificial element: it does not occur naturally. To produce it, it is necessary to expose other substances to an intense neutron flux. It is possible to produce some micrograms of Es 253 through this method. However, its short half live and high alpha-particle emissivity limits its usage. It is also possible to produce Es 254 although in smaller amounts.
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100. Fermium
Fermium is the eighth of the man-made transuranium elements, and the eleventh member of the actinide series. Element 100 was discovered at the same time as element 99 (einsteinium) in 1952. History: During 1949, the preceding two elements, berkelium (97) and californium (98) were synthesized in minute amounts. It was then clear that the synthesis of elements beyond californium could be achieved by two methods: exposing heavy elements to a very high neutron flux, or bombarding them with heavier ions, such as carbon or nitrogen. The Materials Testing Reactor in Idaho came into operation during 1952, and provided a neutron flux an order of magnitude higher than previously available. At the same time, techniques for accelerating useful beams of heavy ions were being developed in several laboratories. These developments ensured the eventual synthesis of elements 99 and 100, but the first observation of these elements came unexpectedly, from a quite unrelated experiment - the explosion of the first thermonuclear bomb in the Pacific during November 1952. Samples of debris were collected by drone aircraft flying through the cloud and analyzed. Among the new activities detected were alpha-emitters of 6.6 and 7.1 MeV, indicating that a brief exposition to a very high neutron flux can have similar results to the slow irradiation by heavy elements made on the labs in Idaho. From the analysis of these samples it was possible to identify the source of the alpha particles with that specific energy as the new elements 99 and 100 respectively. During 1953 and early 1954, while the discovery of elements 99 and 100 was withheld from publication, a group at the Nobel Institute for Physics in Stockholm bombarded U 238 with oxygen-16 ions, and isolated a 30-minute alpha emitter which they tentatively ascribed to a new isotope (250) of element 100, without claiming the discovery of the element. The full story of the discovery of elements 99 and 100 was finally published in mid-1955 by a group of authors of the laboratories involved. Element 99 was named einsteinium, in honor of Albert Einstein, and element 100 was named fermium, in honor of Enrico Fermi. Occurrence: Fermium is an artificial element: it does not occurs naturally. To produce it, it is necessary to expose other substances to an intense neutron flux. The easiest fermium isotopes to produce are, in general, more unstable. The isotope Fm 257 would be much more useful for chemical studies, but it is only produced in very small yield in the highest neutron fluxes available.
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101. Mendelevium
Mendelevium is the ninth element of the transuranians (artificial elements), and it is the twelfth member of the actinides series. History: The element 101 was synthesized for the first time, in 1955, in the Laboratory of Radiation in the University of California, Berkeley. A. Ghiorso, B. G. Harvey, G.R. Choppin, S.G. Thompson and G.T. Seaborg irradiated a small sample of einsteinium with 41 MeV helium ions, observing an isotope of element 101 with mass number 256. These experiences deserve a special reference for the tiny dimension of the irradiated sample (Es 253) and consequently of the obtained product, and for the new irradiation techniques. Initially it was not detected any alpha particle activity that could indicate the presence of element 101; however, spontaneous fission of fermium was observed leading to a new element, proved in subsequent experiences to be the 101st. Based on this evidence, although indirectly, the investigators announced the discovery of element 101, suggesting the name mendelevium, in honor of Dimitri Mendeleev. Originally, the symbol of the mendelevium was Mv, this being later altered to the actual Md. There are registers of producing mendelevium isotopes in the former-U.S.S.R through heavy ions reacting. In 1967 the announcement of the discovery of Md 258 was made. This has a half-life of about two months, being the highest for a mendelevium isotope. Occurrence: Since mendelevium is an artificial element, it does not occur naturally. Its synthesis processes are based on the bombardment of samples of other heavy elements with helium nuclei or heavier ions. Applications: There are no applications of this element because of its instability and shortage.
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102. Nobelium
History: The discovery of nobelium, element 102, is still an unresolved question, since its discovery had been announced by three different research groups. The same technique was employed by all groups working on element 102. The recoil procedure involves irradiating a thin target with heavy ions and then catching the recoil atoms on a foil. This method has several advantages such as the possibility of immediate separation of the short-lived recoil atoms from the intense radioactivity of the target, the ability to do repeated irradiations with the same target and the possibility of adapting the technique to identify the original recoil atoms by collecting recoils from the alpha decay of the initial product atoms. The first group, consisting of scientist from Argonne National Laboratory, USA, Harwell Atomic Energy Research Establishment, England and the Nobel Institute of Physics, Sweden, reported the isolation of element 102 in 1957. This group included P. R. Fields, A. M. Friedman, J. Milstred, H. Atterling, W. Forsling, L. W. Holm and B. Astrom. They irradiated a target of Cm 244, Cm 246 and Cm 248 with C 13 ions, obtaining an isotope with mass number between 251 and 255, but with atomic number considered to be 102. This group proposed the name Nobelium in honor to Alfred Nobel. Approximately one year later, another group of scientists working at the Lawrence Radiations Laboratory, University of California, succeeded in the irradiation of a similar target with C 12 ions. They detected the isotope 254 with a half-life of 3 seconds. This group identified the isotope 255 prepared through the irradiation of Cf 252 with boron ions. The group was composed by the scientists A. Ghiorso, T. Sikkeland, J. R. Walton and S. G. Seaborg. The third group of scientists working in 1957 at the Dubna Institute in the former USSR, also reported the production of isotopes of element 102. Their attempts involving irradiating Pu 239 and Pu 241 with O 16 ions were not very successful. Only in 1963 they were able to report the detection of No 256 through the irradiation of U 238 with Ne 22 ions and using a method similar to the other research groups. Occurrence: Nobelium does not occur in Nature. The amounts produced are quite small due to the instability and were obtained through the irradiation of a target of actinide atoms by heavy ions. Applications: There are no applications to this element due to its instability and scarcity.
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103. Lawrencium
History: In 1961, a group of scientists, constituted by A. Ghiorso, T. Sikkeland, A. E. Larsh and R. M. Latimer, of the Laboratory of Radiation, at the University of California, announced the discovery of the element 103, suggesting the name lawrencium in honor of Ernest O. Lawrence. The irradiation of several isotope of californium with boron ions (B 10 and B 11) and the consequent analysis, using solid state detectors, of the irradiation products revealed a source of alpha particles of 8.6 MeV. They attributed it to the isotope of element 103, with number of mass 257. In 1965 one of the research teams of Dubna Laboratory, in the former-U.S.S.R., announced the synthesis of Lw 256 by irradiation of Am 243 with O 18 ions. Lawrencium is the last element of the actinide series.
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104. Rutherfordium
History: The discovery of this element is disputed by the Institute of Dubna (ex-USSR) and the University of Berkeley research teams. During 1964, the Dubna researchers isolated the element 104, through collision reactions between Pu 242 and Ne 22 ions. They suggested the name Kurchatovium and symbol Ku, in honour of Igor Vasilevich Kurchatov, chief member of the Soviet Nuclear Research. However, in 1969 the Berkeley team succeeded in isolating an isotope of element 104 involving the collision of Cf 249 and C 12. This team proposed the name Rutherfordium (Rf) in honor of the NewZealand born physicist Ernest Rutherford, whose works was crucial to the early understanding of the atomic nucleus. Rutherfordium is now the preferred IUPAC name.
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105. Dubnium
History: The discovery of this element is disputed by the Institute of Dubna (Russia) and the University of Berkeley teams. It appears that it was first prepared independently by the two research teams through collision experiences similar to those that produced Rutherfordium (element 104). In 1967, Flerov reported the existence of element 105, at the Joint Research Institute in Russia, involving collision reactions between Am 243 ions and Ne 22 ions. Later, in 1970, Ghiorso and his coworkers synthesized dubnium at the University of Berkeley (California) in the USA. This method involved the collision of Cf 249 ions with N 15 ions. This element was named Dubnium (Db) in honor to the Dubna laboratory, in Russia.
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106. Seaborgium
History: This element was discovered, in 1974, at the Lawrence Berkeley Laboratory in University of Berkeley, California, USA, by Albert Ghiorso and his co-workers. This element was first prepared in experiments performed both by the Soviet Joint Institute for Nuclear Research and the Berkeley team. The Russian experiments involved the bombardment of lead isotopes with Cr 54 ions while the American performed the collision of O 18 ions with Cf 249 ions. However, it was not until 1993 that its existence was confirmed by the American university. It was named Seaborgium (Sg) in honor of Glenn T. Seaborg, an American chemist who was co-discoverer of 11 artificial elements and Nobel prize winner.
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107. Bohrium
History: This element was discovered, in 1981, at the GSI (Gesellschaft fur Schwerionenforschung Institut), Darmstadt, Germany, by Peter Armbruster, Gottfried Mnzenber and their co-workers. In spite of scientists from ex-USSR had reported the production of an isotope of bohrium in 1976, their work was only confirmed by German workers, in 1981. It was named Bohrium (Bh) in honor of the Danish physicist Niels Bohr, whose research contributed significantly to the modern understanding of the atom.
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108. Hassium
History: This element was discovered, in 1984, at the GSI (Gesellschaft fur Schwerionenforschung Institut), Darmstadt, Germany, Peter Armbruster, Gottfried Mnzenber and their co-workers. It was named Hassium (Hs) for the German state Hesse, where Darmstadt is located.
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109. Meitnerium
History: This element was discovered, in 1982, at the GSI (Gesellschaft fur Schwerionenforschung Institut), Darmstadt, Germany, by Peter Armbruster, Gottfried Mnzenber and their co-workers. The isotope of element 109 which was prepared by the German team, had an atomic mass number of 266. This new element was produced by collision reactions involving Fe 58 and a Bi 209. This was achieved by accelerating the iron atoms to a high energy in the heavy ion accelerator UNILAC at GSI. It was named Meitnerium (Mt) in honor of Lise Meitner, the Austrian physicist who first conceived the idea of nuclear fission.
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110.
History: This element was discovered, in 1994, by S. Hofmann, V. Ninov, F. P. Hessberger, P. Armbruster, H. Folger, G. Mnzenberg, H. J. Schtt, among others. These are researchers at the Gesellschaft fr Schwerionenforschung (GSI) in Darmstadt, Germany. The experiments performed by these researchers led to the production of the first atom of element 110, on the 9th of November 1994. The isotope produced, with atomic mass 169, resulted from collision reactions between nickel and lead isotopes, performed in the heavy ion accelerator UNILAC at GSI. Between 1981 and 1984 the elements 107 (bohrium), 108 (hassium), 109 (meitnerium) were also produced and identified at that institution. Currently, the element is only referred by its IUPAC nomenclature.
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111.
History: This element was discovered, in 1994, by S. Hofmann, V. Ninov, F. P. Hessberger, P. Armbruster, H. Folger, G. Mnzenberg, and among others, at the Gesellschaft fr Schwerionenforschung (GSI) in Darmstadt, Germany. This element was produced through collision reactions between Bi 209 and Ni 64, in the heavy ion accelerator UNILAC at GSI. Currently, the element is only referred by its IUPAC nomenclature.
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112.
History: This element was discovered, in 1996, by S. Hofmann, V. Ninov, F. P. Hessberger, P. Armbruster, H. Folger, G. Mnzenberg, and among others, at the Gesellschaft fr Schwerionenforschung (GSI) in Darmstadt, Germany. This element was produced, on 9th February 1996 at 22:37, through collision reactions between zinc and lead atoms, in the heavy ion accelerator UNILAC at GSI. It is the heaviest atom ever produced by man, being the isotope produced 277 times heavier than hydrogen. Currently, the element is only referred by its IUPAC nomenclature.
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Bibliografia a) "Making New Elements", Peter Armbruster and Fritz Peter Hessberger, Scientific American, Sept. 1998, pp 50-55
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Chemical Elements

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