ARTICLE AN INTRODUCTION TO THE HISTORY OF CHEMISTRY N. R. DAS* The word chemistry originated from the term, chemi or kima, the name of Egypt in Egyptian. The time period for the history of chemistry covers from ancient history of chemistry to the present. In earliest civilizations, fire was accepted as a mystical force and the controlled use fire in their familiar regular practices like cooking, lighting, making of earthen and glass wares, medicines, wines, metallurgy, armours, etc. eventually resulted in the development of various branches of chemistry in the later period. The basic chemical hypothesis was first propounded by Aristotle with his theory of four fundamental elements, fire, earth, water and air, from which everything was formed as a combination. In medieval alchemy around 300 B. C., the arts of alchemy being intermingled with magic and occultism proliferated into natural science with the goal of transmuting cheap metals into precious gold with ‘Philosopher’s Stone’ and of chemical concoction, ‘The Elixir of Life’, for a longer and cured life. In seventeenth century, Robert Boyle was the first to make a clear differentiation between alchemy and scientific experimental approach towards matter initiating the trend of the history of modern chemistry. The pioneering contributions of Antoine Lavoisier and Jons Berzelius established the subject of chemistry on proper experimental and theoretical footings of chemical science. In the later period, with important discoveries and rapid advancement in research and technologies, in general, the subject of chemistry has been expanded into different broad groups as well as in cross-disciplinary and specialized fields of chemical science depending on the type and kind of matter being investigated. Chemistry is now a major branch of physical science. Introduction I n early civilizations, thinkers were those who always search for the logic regarding the existence of the surrounding materials and tried to identify the basic elements comprising the natural substances. The ancient Greek, Indian, Mayan, Chinese and other philosophies attempted to postulate appropriate hypothesis for the existence of the natural materials in solid, liquid or gaseous phases having different characteristic properties of density, colour, smell, etc. as well as their changing behaviours in the prevailing environmental conditions. In the history of chemistry as early as around 300 B. C., the regular skilful practices involving various techniques * 342 Former Professor, Saha Institute of Nuclear Physics, 1/AF, Bidhan Nagar, Kolkata - 700 064, e-mail : [email protected] of chemistry, medicine, metallurgy, astronomy, philosophy, astrology and mysticism, as parts of normal behaviour in different regions of the world, were known as Alchemy. An alchemist was later designated as a ‘chemist’ and in describing the activities of the chemists, the suffix ‘-ry’ was added to the word chemist, to assign the subject as ‘chemistry’. The etymology or the origin of the word chemistry is much disputed as the science of chemistry has been around since the prehistoric times. The visions on the composition and properties of matter were to some extent shared by both alchemy and chemistry and a blend of these was presented earlier by the term chymistry. Robert Boyle in 1661 was the first to use the term chymistry to specify the subject dealing with the material principles of mixed bodies. According to Christopher Glaser (1663), chymistry SCIENCE AND CULTURE, NOVEMBER-DECEMBER, 2016 meant to acquire scientific knowledge of dissolving a substance, to draw from it another substance of different composition and to exalt it to a higher perfection. In 1730, Georg Ernst Stahl was perhaps the first to use the word chemistry to describe the technique of resolving mixed, aggregate or compound materials into their principles and of composing these materials from those principles. JeanBaptiste Dumas in 1837 referred chemistry to deal with the science concerning the laws and the effects of molecular forces. In retrospect, with new discoveries and development of theories in chemical science, the definition of chemistry has gradually been modified over the period. For example, Linus Pauling in 1947 suggested that the chemistry is to deal with the science of substances involving their structure, properties and the reactions that change them into other substances. More recently in 1998, the definition of chemistry has been broadly modified to mean the study of matter and the changes it undergoes, as phrased by Professor Raymond Chang. The subject of chemistry has now become a major branch of physical science primarily concerned with atoms, molecules and their interactions and transformations involving the structure, composition and properties of matter. With rapid advancement of science, the subject of chemistry, in the later period, has become intertwined with the modern topic like thermodynamics, nuclear science and many other fields of advanced research, particularly, in occupying an intermediate position between physics and biology. In this article, the time span for the History of Chemistry representing from the ancient period to the present is chronologically classified into four broad categories such as Ancient Period of the History of Chemistry, Medieval Alchemy, Early Chemistry of 17th and 18th Centuries, and Chemistry of 19th Century to the Present. Ancient Period of History The earliest evidence of using metal by humans as free ‘native’ gold has been manifested from the fact that small amounts of natural gold have been found in Spanish caves of the late Paleolithic period of around 40,000 B. C. In ancient Egypt, as early as in 2900 B.C., gold was considered as precious metal and the metals like silver, copper, tin which can also be sometimes found native were used in metal working in the prevailing cultures. Egyptian weapons made from meteoric iron in about 3000 B.C. were known as ‘Daggers from Heaven’. In early societies, the fire that was generally utilized to transform one substance into another producing heat and VOL. 82, NOS. 11–12 light was accepted simply as a mystical force. Early evidence of extractive metallurgy dated fifth and sixth millennium B. C. involving lead and copper was found in different archaeological sites in Siberia and of the third millennium B. C. in Portugal, Spain and United Kingdom. The controlled use of fire in various aspects of cooking and habitat lighting; making of glass and earthen wares like pottery, bricks, glazes; fermentation of beers and wines; preparation of medicines, soaps, perfumes; extraction of chemicals from plants; etc. eventually formed the basis for development of different branches of chemistry in the later period of around 1000 B. C. The application of fire for extraction and purification of metals from ores, production of alloys like bronze, making of armors and weapons for the armies from superior alloys, etc. resulted in the initiation of the field of metallurgy which helped in the development of early human culture. In the Bronze Age around 3500 B.C., significant progress in alchemy involving metallurgy was achieved in ancient India. The Iron Age began with the development of the method for extraction of metal iron from its ores by Hittites in about 1200 B.C. Wide varieties of evidences of early civilizations in different regions of the world particularly in ancient and medieval kingdoms and empires of the Middle East, Iran, Egypt, Anatolia (Turkey), Greeks, Romans, Europe, China, India, Japan, amongst others, have indicated the cultural developments in this age period. The new prehistoric discoveries are continuous and ongoing. The early theory of atomism has been traced back to ancient Greece and ancient India. The Greek philosophers, Democritus and Epicurus, around 440 B.C, proclaimed that the simplest unit of matter is the atom and all matter is composed of these indivisible and indestructible atoms. The proclamation was found to be corroborated with the views of the Indian philosopher, Kanada, the founder of the Vaisheshika philosophy, around the same time period. In 380 B. C, the Greek thinker, Polybus postulated that the human body is composed of four humours, the four fluids of the body, believed to determine the physical and mental qualities of human. Epicurus around 300 B.C. suggested a universe of indestructible atoms in which man himself has the capability of achieving a balanced life. In early civilizations, the familiar practices of arts or the skilled techniques were followed without any basic knowledge or a systematic concept. In 300 B.C., a chemical hypothesis was first propounded by Aristotle in Greece with the theory of four fundamental elements, fire (hot and dry), water (cold and moist), air (hot and moist) and earth (cold and dry), as presented in Figure 1, in which everything was considered to be formed as a combination of these 343 elements. Empedocles also hinted a hypothesis about the theory of fundamental elements earlier in 420 B. C. The Roman poet and philosopher Lucretius in 50 B. C. wrote ‘De Rerum Natura (The Nature of Things)’ which described the principles of atomism; the nature of mind and soul; cause of sensation and thought; the development of the world and explanations for a variety of celestial and terrestrial phenomena. Fire Water Air Earth Figure 1. Symbol of basic alchemy Medieval Alchemy The word alchemy was derived from the Arabic synonym, al-kîmîâ which might have been originated from the word Chemi or Kimi, the ancient name of Egypt in Egyptian. In the Hellenistic world, (related to Greek culture from 323 B. C. to 31 B.C.), the art of alchemy being intermingled with magic and occultism proliferated first into the study of natural substances with the ultimate goal of transmuting common cheap metals into attractive gold or silver with ‘Philosopher’s Stone’ and inventing a chemical concoction, ‘The Elixir of Life’, that would enable people to live longer and cure all ailments. In alchemy, known metals were considered in conjunction with heavenly bodies. The advent of alchemy was greatly influenced by the Aristotle’s theory of four fundamental elements along with two more alchemical elements, namely, sulfur, as ‘the stone which burns’ symbolizing the properties of flammability or combustion, and mercury, characterizing the properties of volatility and stability, and in addition, salt indicated the solidity. According to Swiss alchemist Paracelsus, the four element theory of Aristotle appeared in bodies as three fundamental metallic principles, the ‘tria prima’ of the alchemists. In medieval alchemy during 300 B. C. to 300 A.D., the Persian alchemist, Jabir bin Hayyan, as ‘the father of chemistry’, led the foundations of a systematic scientific approach towards the development of experimental chemical research in the Arab World. Attempts were made for classification of the alchemical processes and for development of different experimental apparatus. In ancient India, the chemical excellence in various aspects of scientific developments was highly acclaimed and was far 344 ahead of many of the existing civilizations during the period. In ninth century, the inventions of laboratory apparatus like alembic (apparatus for distilling), crucible, retort, furnace; chemical analysis of substances; distinction between acids and alkalis; manufacture of drugs; etc. were achieved in chemistry. Alchemy made extensive contribution to the evolution of chemistry in Greco-Roman Egypt, India and the Arab world and the Western alchemists, in general, became influenced by the scientific experimental framework developed in these regions, as the discipline migrated to Renaissance Europe in twelfth century. In Europe, Paracelsus (1493–1541) refuted the four element theory of Aristotle and introduced a hybrid of alchemy and science called as iatrochemistry. In 1556, Georg Agricola, known as the ‘father of metallurgy’, through his presentation of the processes for mining of metal ores and refining of metals by smelting in ‘De re metallica’, tried to remove the mysticism associated with the subject. Several chemists contradicted the theories of alchemy and hinted for the version of the conservation of mass suggesting that a material body is capable of changing but can’t disappear. A fraudulent side of alchemy was exposed, especially in manufacturing of counterfeit gold from cheap substances, in ‘Canon’s Yeoman’s Tale’ of Geoffrey Chaucer. In 1317, the Avignon Pope John XXII ordered the alchemists to leave France for the misdeeds. In England in 1403 the act of ‘multiplication of metals’ was declared punishable by death. In spite of such extreme measures, some group of alchemists still sought to discover the ‘philosopher’s stone’ and ‘the elixir of life’, which, however, never happened within the time period. In alchemy, the alchemists although were not so successful in elucidating the nature of matter or its transformation, but have set the trend of modern chemistry. Since the beginning of the fourteenth century, the alchemists in general became more conscious about the reproducibility of the scientific methods and experiments and felt the need of specific vocabulary for systematic naming of the new compounds and the invented terminologies. During the period, along with popular exotic alchemy, the spiritual alchemy was also flourished and realigned to its Platonic, Hermetic and Gnostic roots and the symbolic quest for the philosopher’s stone still continued to be the domain of several respected scientists and intellectuals until the early eighteenth century. Some of the early renowned modern alchemists include Jan Baptist van Helmont, Robert Boyle and Isaac Newton. SCIENCE AND CULTURE, NOVEMBER-DECEMBER, 2016 Early Chemistry of 17th and 18th Centuries Roger Francis Bacon in 1605 in his book, ‘The Proficiency and Advancement of Learning’, presented an outline of the scientific methods developed during the period. Michal Sedziwoj in his alchemical treatise, ‘A New Light of Alchemy’, in the same year, indicted the presence of the ‘food of life’ in the air, later identified as oxygen. Jean Beguin described the first-ever chemical equation in his book, ‘Tyrocinium Chymicum’, in 1615. Rene Descartes in 1637 presented a detailed description of the existing scientific methods in his publication, ‘Discours de la method’. A group of chemists, namely, Robert Boyle, Robert Hooke and John Mayow, at Oxford being encouraged by the new concept of the empirical methods propounded by Bacon and others, began to reshape the old alchemical traditions into an organized scientific discipline of chemistry. Robert Boyle (1627–1691) made a clear differentiation between the activities of alchemy and the scientific experimental approach towards matter initiating the beginning of the history of modern chemistry. He believed that the developed scientific methods denied the limitation of chemical elements to only the four classical elements of Aristotle and put forward a mechanistic alternative of atoms and chemical reactions that could be the subject of rigorous experiment. He suggested that all theories must be experimentally proved before being accepted as true. His work was involved with some of the modern ideas of atoms, molecules and chemical reactions. He favored the word corpuscle as finest division of matter over atom. The book, ‘The Sceptical Chymist’, in which he proposed the hypothesis that every phenomenon is the result of collisions of particles in motion acted as a landmark publication in the field of chemistry. He is however best known for his Boyle’s Law introduced in 1662 describing the relationship between the pressure and volume of a gas under different experimental conditions. Robert Boyle for his pioneering contributions in chemical science is regarded as the Founding Father of Modern Chemistry. During the period, it became evident that ‘air’ is comprised of different gases. Jan Baptist van Helmont coined the word ‘gas’ from the Greek word chaos in naming some insubstantial substances present in the ‘air’ and is remembered today as the founder of pneumatic chemistry. In 1754, Helmont along with Joseph Black discovered carbon dioxide, called as ‘fixed air’. Helmont in his work, Ortus medicinae, in 1648 proposed an early version of the Law of conservation of mass. Black in 1758 VOL. 82, NOS. 11–12 formulated the concept of latent heat to explain the thermochemistry of phase changes. In 1702, German chemist Georg Stahl assigned the name ‘phlogiston’ to the substance believed to be released in the process of burning. J. J. Beecher proposed that in the process of burning of a substance, phlogiston is added to the flame of the burning object from air, in some cases, producing a product. The English chemist Henry Cavendish in 1766 discovered the colorless and odorless gas, hydrogen, as ‘inflammable air’ which burns and can form an explosive mixture with air. In 1774, the English chemist Joseph Priestley isolated pure oxygen as ‘dephlogisticated air’, the existence of which was indicated earlier in 1773 by the Swedish chemist Carl Wilhelm Scheele as ‘fire air’. Cavendish suggested that oxygen is a part of air that combines with substances as they burn. Priestley is also credited for the discovery of soda water and several other ‘airs’ (gases). In eighteenth century, the French chemist AntoineLaurent de Lavoisier through his pioneering research and development in chemistry established the subject on proper theoretical footings. He proposed that air is composed of two parts, namely, oxygen (Greek for acid-former) which combines with metals to form calxes (powdery substance) and the azote (Greek for no life). Lavoisier in his ‘Considérations Générales sur la Nature des Acides (1778)’ indicated that the ‘air’ responsible for combustion, was the source of acidity and all acids contained oxygen. He also demonstrated that the ‘inflammable air’ (hydrogen) combined with the ‘dephlogisticated air’ (oxygen) to produce a dew appeared to be water. Mikhail Lomonosov in Russia anticipated the kinetic theory of gases during the period. Lavoisier with Pierre-Simon Laplace in 1782-83 introduced a technique for determination of the heat involved in various chemical changes using an icecalorimeter leading to the foundation of thermo-chemistry. In 1787, Lavoisier and Claude Louis Berthollet in their ‘Methods of Chemical Nomenclature’ described a new system of chemical nomenclature for the chemical compounds such as sulfuric acid, sulfates and sulfites still in use today. Lavoisier in his publication, ‘Traite Elementaire de Chimie (Elementary Treatise of Chemistry, 1789)’, which is considered as the first modern chemical text book, presented a new theory as ‘Lavoisier’s Law’ elucidating the principle of conservation of mass. He believed in the theory of radicals which functions as a single group in a chemical reaction. He also indicated that 345 diamond is a crystalline form of carbon. Lavoisier introduced the use of chemical balance in the laboratory. Lavoisier through his fundamental scientific contributions towards systematic chemical experimentations and their quantitative way of presentation brought about a revolution in chemical science. He observed, “I have tried...to arrive at the truth by linking up facts; to suppress as much as possible the use of reasoning, which is often an unreliable instrument which deceives us, in order to follow as much as possible the torch of observation and of experiment.” Lavoisier is celebrated as the ‘father of modern chemistry’ and a chemical analogue of Isaac Newton in physics. During the period, the elements, cobalt, nickel and tungsten, were respectively identified by the Swedish chemist Georg Brandt in 1735, Axel Fredrik Cronstedt in 1751 and Lose and Fausto Elhuyar in 1783. Axel Fredrik Cronstedt is considered as one of the founders of modern mineralogy. Louis Claude Cadet de Gassicourt synthesized the first organometallic compound, namely, cacodyl oxide in 1757. Berthelot in 1785 produced the strong chlorine oxidant, potassium chlorate (KClO3), as Berthelot’s salt and also determined the elemental composition of ammonia. He also introduced the theory of chemical equilibrium. The Italian physicist Alessandro Volta in 1784 while investigating ‘animal electricity’ discovered by Luigi Galvani utilizing frog leg as a detector devised an electrochemical cell that derived electrical energy from spontaneous redox reaction taking place within the cell. Volta thus developed the electrochemical theory of chemical combinations and became the founder of electrochemistry. Michael Faraday through his studies on electro-deposition of metals associated with quantities of chemical elements during electrolysis, made a major contribution to electrochemistry and provided important clues in elucidating the atomic nature of matter. Chemistry of 19th Century to the Present In 1801-1802, the French chemist Joseph Louis GayLussac in his ‘Charles’s Law’ proposed that equal volumes of all gases expand equally with the same increase in temperature. Later in 1808, Gay-Lussac deduced ‘GayLussac’s Law’ or the ‘Law of Combining Volumes’ suggesting that gases at constant temperature and pressure combine in simple numerical proportions by volume and the resulting product or products bear a simple proportion by volume to the volumes of the reactants. Gay-Lussac along with Louis Jacques Thenard identified the element boron through decomposition of boric acid. 346 The English chemist John Dalton in 1803 described the relationship between the components in a mixture of gases and the relative pressure each contributes to that of the overall mixture as Dalton’s law of partial pressures. Dalton in his ‘New System of Chemical Philosophy (18081827)’ outlined the modern views on the atomic theory and suggested that all matters are composed of small indivisible ‘atoms’ and different atoms have different atomic weights and also stressed that the chemical elements combine in integral ratios which is known as ‘Dalton’s Law of multiple proportions’. French chemist Joseph Proust in1804 proposed the ‘Law of definite proportions’ which states that elements always combine in small and whole number ratios to form compounds. The two laws, the ‘Law of multiple proportions’ and the ‘Law of definite proportions’, form the basis of the development of stoichiometry, the term introduced by J. Benjamin Richter. The English chemist Jons Jacob Berzelius in his publication, ‘Lärbok i Kemien’, in 1808 introduced the classical system of chemical symbols and notation. The elements were abbreviated by one or two letters, for example, O for oxygen, Fe for iron, etc. and the elemental proportions in a compound were noted by numbers, the same basic system used today. However, in presenting the formula of a compound, Berzelius used a superscript number, e.g., H2O, instead of the subscript used today, e.g., H 2 O. He also developed the theory of chemical combination suggesting that reactions occur with stable groups of atoms called radicals. His work on precise determination of elementary constituents of large numbers of compounds provided evidence in favor of Dalton’s atomic theory that inorganic chemical compounds are composed of atoms combined in whole number amounts. Berzelius discovered the elements, silicon, selenium, thorium and cerium, and the elements, lithium and vanadium, were identified by his associates. He tried to compile a table of the known elements on the basis of their relative atomic weights in 1828. He believed that salts are compounds of an acid and a base, and also indicated that the anions in acids would be attracted to a positive electrode (the anode) and the cations in bases to a negative electrode (the cathode). He introduced the chemical terms, catalysis, polymer, isomer and allotrope, although the original definitions sometimes differ from modern usage. Friedrich Wohler and the German chemist Justus von Liebig in 1825 confirmed the concept of isomerism suggesting that it is caused by differing in arrangements of the atoms within a molecular structure. Berzelius for his original contributions in science of chemistry is known as the father of modern chemistry along with Lavoisier and Boyle. SCIENCE AND CULTURE, NOVEMBER-DECEMBER, 2016 The English chemist Humphrey Davy, as one of the pioneers in the field of electrolysis, discovered nine new elements including the alkali metals, sodium and potassium, and the alkaline earth metals, magnesium, strontium and barium. In 1810, he renamed the ‘dephlogisticated marine acid’, discovered earlier by Carl Wilhelm Scheele in 1774, as the element, chlorine. Scheele also gave a hint for the formation of aqua regia and identified nitrous oxide known as laughing gas simply by inhaling. The French chemist Bernard Courtois discovered the element iodine in 1811. In 1815, Davy invented the Davy lamp, which allowed the miners to work safely in the coal mines in presence of flammable gases like methane but did not patent it for the benefit of the workers. The Italian physicist Amedeo Avogadro in his ‘Avogadro’s law’ in 1811 postulated that under control conditions of temperature and pressure, equal volumes of gases contain equal number of molecules. He also suggested that simple gases are compound molecules of two or more atoms and not of solitary atoms. In 1850s, several chemists like Alexander Williamson in England, Charles Gerhardt and Charles-Adolphe Wurtz in France and August Kekule in Germany, advocated for reformation of theoretical chemistry to make it consistent with Avogadro hypothesis. Stanislao Cannizzaro constructed a systematic theoretical structural concept that fit almost all of the available empirical evidences and suggested that most of the elementary gases are diatomic, some are monatomic and a few are more complex. He also proposed a relation among equivalent weight, atomic weight and molecular weight on the basis of Avogadro’s hypothesis. Johann Josef Loschmidt in 1865 predicted the exact number of molecules in a mole, later named as Avogadro’s number. The synthesis of the organic compounds, urea, by Friedrich Wöhler in 1828 and acetic acid by Hermann Kolbe in 1847 completely from inorganic sources, helped in making an essential distinction between organic and inorganic substances in chemistry. In 1827, William Prout classified bio-molecules into their modern groupings of carbohydrates, proteins and lipids. Wöhler and Justus von Liebig explained functional groups and radicals in relation to organic chemistry in 1832. By the end of the century, hundreds of organic compounds like synthetic dyes, drugs, etc. have been synthesized. Liebig, in addition to his work in organic chemistry, also made major contributions to agricultural and biological chemistry. The German chemist Liebig for his contributions involving the discovery of nitrogen as an essential plant nutrient and formulation of the ‘Law of the Minimum’ dealing with the VOL. 82, NOS. 11–12 effect of individual nutrients on crops, is considered as the ‘father of fertilizer industry’. Germain Hess in his law of conservation of energy, known as ‘Hess’s law’, in 1840 established that the energy change in a chemical process depends on the states of the starting and product materials only and not on the specific reaction pathway between the two states. In 1864, Cato Maximilian Guldberg and Peter Waage proposed the ‘Law of mass action’. Louis Pasteur in 1849 suggested that the racemic form of tartaric acid is a mixture of the levorotatory and dextrorotatory forms, thus identifying the nature of optical rotation which led to the initiation of the field of stereochemistry. In 1873, Jacobus Henricus van’t Hoff and Joseph Ahille Le Bel independently developed the model for chemical bonding and studied optical activity in chiral compounds. The concept of the ‘asymmetrical carbon atom’ provided an explanation for the occurrence of numerous isomers. William Thomson, better known as Lord Kelvin, in 1848 introduced the concept of absolute zero, the temperature at which all molecular motion ceases. In 1852, August Beer, on the basis of the work of Pierre Bouger and Johann Heinrich, proposed the ‘Beer’s law’ which explains the relationship between the composition of a mixture and the amount of light it absorbs leading to the development of the important analytical technique of spectrophotometry. The technique of spectroscopy was effectively utilized by Robert Bunsen and Gustav Kirchhoff (1859-60) to discover the elements, caesium and rubidium, and the British chemist Crookes to identify thallium in some seleniferous deposits in 1861. Benjamin Silliman Jr. in 1855 developed the methods of petroleum cracking initiating research in the field of modern petrochemical industry. The refinement of petroleum extracted from earth provided a host of liquid fuels such as gasoline, diesel, solvents, lubricants, waxes and many other common materials of the modern world, such as synthetic fibers, plastics, paints, detergents, pharmaceuticals, adhesives and ammonia as fertilizer. The preparation of the dye, mauveine or Perkin’s mauve, by Sir William Henry Perkin in 1856 and that of indigo dye by Adolf von Baeyer from coal tar in 1865, formed the milestone for the synthesis of dyes in industrial organic chemistry. Similarly, in 1862, Alexander Parks synthesized a new synthetic polymer, Parkesine, leading to the foundation of the modern plastics industry. One of the first commercially available plastics, Bakelite, was invented by Leo Baekeland during the period. 347 The German chemist August Kekule von Stradonitz in his book, Lehrbuch der organischen Chemie (Textbook of Organic Chemistry), in 1859 indicated that tetravalent carbon atoms can link together to form a ‘carbon chain’ or a ‘carbon skeleton’, to which other atoms like hydrogen, oxygen, nitrogen and chlorine can be attached. In 1865, Kekulé established the cyclic structure of benzene as a six carbon ring with alternate single and double bonds and described the nature of the aromatic compounds based on benzene molecule. The Swedish chemist Alfred Nobel prepared an explosive compound, nitroglycerin, incorporated in a safer inert absorbent like kieselguhr (diatomaceous earth) and patented as dynamite in 1867. Nobel later developed a more powerful explosive than dynamite, a transparent jelly-like substance, Gelignite or blasting gelatin, in 1876. In nineteenth century, several scientists in facilitating their studies in science felt the need to classify and systematically arrange the elements already discovered during the period. In 1815, William Prout was the first to propose for arrangement of the elements in order of their atomic weights as the atomic weights of the known elements were found to be the exact multiples of the atomic weight of hydrogen. Johann Wolfgang Dobereiner in 1817 tried to draw a relation between the atomic weights and the properties of the elements through his concept of ‘triad’. Berzelius in 1828 compiled a table of relative atomic weights of 43 known elements setting the weight of oxygen exactly equal to 100. In 1862, Beguyer de Chancourtois tried to arrange the elements in the order of their ascending atomic weights in a telluric helix form, a three-dimensional version of the periodic table. John A. R. Newlands in 196365 devised the ‘law of octaves’ which was further modified by Luther Myer of Germany to organize the elements in a periodic table in 1864. The Russian chemist Dmitri Mendeleev made a breakthrough in devising a systematic periodic classification of the 66 known chemical elements in the ascending order of their atomic weights in the modern form of the Periodic Table. The periodic table published in his Principles of Chemistry in 1869, displayed a recurring pattern or periodicity of properties within groups of the known elements. In the later version of his periodic table published in 1871, he confidently predicted the positions and the likely properties of three yet-to-be-discovered elements, designated as eka-boron (Eb), eka-aluminum (Ea) and ekasilicon (Es). The predictions for the yet-to-be discovered elements were proved to be the properties of the elements, scandium, gallium and germanium, respectively discovered 348 later and each of which filled the assigned position in the periodic table. In 1894, Scottish chemist William Ramsay and Lord Rayleigh discovered the monatomic and chemically inert gaseous element argon in air. In the following year, Ramsay identified another inert gaseous element from cleveite mineral and named it as helium, the presence of which was indicated earlier in the solar spectrum. Ramsay and the British chemist Morris W. Travers in 1898 isolated three more inert gaseous elements, neon, krypton and xenon, from air. The discovery of the inert gases, later called as noble gases, resulted in completion of the basic structure of the periodic table. In designing the periodic table, the great visionary, Dmitri Mendeleev, as an icon in science embodied the most fundamental principles lying at the core of the subject of chemistry. Antonius Van den Broek in 1911 suggested that the elements would be more properly organized in the periodic table if the elements were arranged on the basis of their positive nuclear charges rather than that of their atomic weights. In 1913, Henry Moseley following the work of Broek introduced the concept of atomic number and proposed that the properties of the elements are periodic functions of their atomic numbers and not atomic weights as indicated by Mendeleev and others. Presently, to identify the periodic trends, the chemical elements are arranged in groups or columns and periods or rows primarily based on the increasing orders of their atomic numbers in the periodic table. With wide acceptance, the periodic law and the table have now become the basic framework for a great part of chemical science. American physicist J. Willard Gibbs in his study on thermodynamic, introduced the concept of chemical potential or the ‘fuel’ that makes chemical reactions to take place. In Gibbs’ phase rule, he included almost all the variables like temperature, pressure, energy, volume and entropy generally involved in a chemical reaction. In 1884, van’t Hoff proposed a general thermo-dynamical relationship between the heat of conversion and the displacement of equilibrium as a result of temperature variation in chemical kinetics. The concept of this mobile equilibrium was subsequently modified by Henry Louis Le Chatelier in 1885 through the ‘van’t Hoff-Le Chatelier principle’ or simply ‘Le Chatelier’s principle’. The application of thermodynamics to chemistry by Gibbs and others was instrumental in transforming physical chemistry into an important branch of deductive science in chemistry. SCIENCE AND CULTURE, NOVEMBER-DECEMBER, 2016 Hermann Emil Fischer (1884-86) studied the chemistry of glucose and related sugar and also synthesized and proposed the structure of purine, a key structure in different bio-molecules. Alfred Werner through his work on the octahedral structure of cobalt complexes established the field of co-ordination chemistry in 1893. In the last decade of the nineteenth century, several landmark discoveries on the sub-atomic particles and the atomic structure encouraged the scientists in initiating a new field of research in Nuclear Science. J. J. Thomson in 1897 discovered the negatively charged particle, electron, the first particle to be recognized as a constituent of all atoms using the cathode ray tube. Eugene Goldstein in 1886 and Wilhelm Wien in 1898 predicted the existence of the positively charged particle as canal rays or positive rays (streams of positive ions) with a charge equal and opposite to the negatively charged electron and Rutherford in 1920 suggested the name, proton, for this positively charged particle. The electrically neutral nuclear particle, neutron, was however, discovered later by James Chadwick in 1932. Studies on canal rays by Wien in 1898 led to the development of the important analytical technique of mass spectrometry. During the period, Wilhelm Conrad Roentgen while working on the effect of cathode rays on barium platinocyanide, discovered X-rays in 1895. Similarly, in 1896, Henri Becquerel in his studies on fluorescence with potassium uranyl sulfate observed that the salt emits a fluorescent light with or without the aid of sunlight and he termed it as ‘Becquerel Rays’ or ‘Uranic Rays”. Thus, the phenomenon of radioactivity was discovered and the term ‘radioactivity’ was first used by Polish-born Marie Sk³odowska Curie. Marie Curie along with her husband, French physicist Pierre Curie in 1898 discovered two new radioactive elements, radium and polonium, in pitchblende mineral through their nuclear properties of radioactivity. Earnest Rutherford in 1906 developed an atomic model, known as ‘Rutherford model’, which was later modified by Danish physicist Niels Bohr and Henry Moseley. In 1911, Rutherford while studying the characteristic properties of radioactivity, discovered three types of radiations, namely, alpha particles (α, positively charged), beta particles (β, negatively charged) and gamma rays (γ, neutral electromagnetic radiation) and also demonstrated that atoms of one radioactive element would spontaneously turn into atoms of another element with emission of radiation. Bohr in 1913 introduced the concept of quantum mechanics to atomic structure through his ‘Bohr model’. He also postulated that electromagnetic radiation VOL. 82, NOS. 11–12 is absorbed or emitted when an electron moves from one orbit to another producing a characteristic emission spectrum for the element. Frederick Soddy introduced the concept of isotopes in 1913 and also discovered the element protactinium in 1917. Rutherford in 1919 reported the discovery of artificially induced nuclear transmutation, the dream of the earlier alchemists, through a nuclear reaction between nitrogen atoms and alpha particles producing oxygen atoms and protons, represented as 14N(α, p)17O. During the period, different advanced nuclear devices like the cyclotron conceived by E. O, Lawrence in 1929 and the electrostatic accelerator built by Cockcroft and Walton in 1932 for accelerating nuclear particles as projectiles to cause nuclear transmutation were invented. Irene Curie-Joliot and her husband Frederic Joliot in 1934 demonstrated that radioactive elements could be created artificially in the laboratory. The German scientist Otto Hahn along with his coworkers in 1939 discovered the neutron induced nuclear fission resulting in release of a large amount of nuclear energy. In USA, the Manhattan Project was in process at the University of Chicago and the very first nuclear fission reactor was developed under the leadership of Enrico Fermi in 1940. The important discoveries and outstanding achievements in nuclear science since the last decade of the nineteenth century, in general, resulted in the development of a new branch of chemistry in chemical science, namely, nuclear chemistry. In the beginning of the twentieth century, the American scientists Linus Pauling and Gilbert N Lewis established the electronic theory of chemical bonds and molecular orbital, known as ‘valence bond theory’. In 1902, Lewis suggested that the chemical bonds are formed through the transference of electrons in the outermost ‘valence’ shell of the atom, to give each atom a complete set of eight outer electrons (an ‘octet’). In the article ‘The Atom of the Molecule’ in 1916, he indicated that a chemical bond is formed by a pair of electrons shared by two atoms and also introduced the ‘electron dot diagrams’ to symbolize the electronic structures of atoms and molecules, now known as ‘Lewis structures’. Subsequently, American chemist Irving Langmuir in1919 introduced the term covalent bond. In 1920s, the Lewis’s model of the electronpair bond was effectively applied by the British chemists Arthur Lapworth, Robert Robinson, Thomas Lowry and Christopher Ingold in organic chemistry and the American chemist Maurice Huggins and the British chemist Nevil Sidgwick in coordination chemistry. In 1912, Peter Debye developed the concept of molecular dipole to 349 describe asymmetric charge distribution in some molecules. In 1923, Lewis and M. Randall published ‘Thermodynamics and the Free Energy of Chemical Substances’, the first modern treatise on chemical thermodynamics. Lewis developed the electron pair theory of acids and bases in which an acid as any atom or molecule with an incomplete octet is capable of accepting electrons from another atom and a base is, of course, an electron donor. In 1909, S. P. L. Sorensen developed the concept of pH in measuring acidity. Svante Arrhenius in his acid-base theory stated that an acid is a substance that produces hydronium ion when it is dissolved in water and a base is one that produces hydroxide ion in water. Acidity based on Brønsted–Lowry definition was expressed as the acid dissociation constant (Ka) which measures the relative ability of a substance to act as an acid. The important analytical technique, chromatography, was invented by Mikhail Tsvet in 1903. The development of the Haber or Haber-Bosch process by Fritz Haber and Carl Bosch in 1905 for preparation of ammonia through combination of nitrogen and hydrogen has become an important landmark in industrial chemistry with deep consequences in agricultural production of fertilizers and munitions. Haber has been considered as the ‘father of chemical warfare’ for his work on deploying chlorine and other poisonous gases during World War I. In 1912, William Henry Bragg and William Lawrence Bragg proposed ‘Bragg’s law’ and developed the technique of X-ray crystallography, effectively utilized as a tool in elucidating the crystal structure of substances. In 1924, the French quantum physicist Louis de Broglie introduced the theory of electron waves based on ‘wave-particle duality’ in which he proposed that particles can behave like waves and waves (radiation) can behave like particles. In 1926, Austrian physicist Erwin Schrödinger on the basis of the wave-particle duality theory introduced a wave equation, known as the Schrodinger equation. Austrian-born physicist Wolfgang Pauli in 1925 through his ‘Pauli Exclusion Principle’ which states that no two electrons around a single nucleus in an atom can occupy the same quantum state simultaneously, made major contributions to the development of the quantum mechanics and quantum field theory. German physicist Werner Heisenberg in formulating quantum mechanics in terms of matrices introduced his ‘uncertainty principle’ regarding the status of an electron in an atom in 1927. Studies on the application of quantum mechanics to the diatomic hydrogen molecule and the phenomenon of the chemical bond by Walter Heitler and Fritz London in 1927 are often 350 considered as the milestones in the history of quantum chemistry. In 1953, the heuristic approach of James Watson and Francis Crick in deducing the double helical structure of DNA capable of explaining by the knowledge of chemistry and the X-ray diffraction patterns, led to an explosion of research in the field of biochemistry. The development of the method of polymerase chain reaction (PCR) by Kary Mullis in 1983 for in-vitro amplification of DNA in the laboratory has made possible the study of sequence of DNA of organisms culminating in the growth of the human genome project. Miller-Urey demonstrated that the basic constituents of proteins and amino acids could themselves be built up from simpler molecules in a simulation of primordial processes on earth and this was perhaps the first attempt by chemists to study hypothetical processes of the origin of life in the laboratory under controlled conditions. Harold Kroto, Robert Curl and Richard Smalley in 1985 discovered fullerenes, a class of large carbon molecules, superficially resembling the geodesic dome. The carbon nanotube, a cylindrical type of fullerene, invented through electron microscopy by Sumio Lijima in 1991, is being used as an important component in the field of nanotechnology. In 1970, John Pople developed the Gaussian program suitably applied to computational chemistry. Eric Cornell and Carl Wieman in 1995 produced the first Bose-Einstein condensate, a substance that displays quantum mechanical properties on the macroscopic scale. In mid-twentieth century, chemical investigations on the quality and purity of the intrinsic semiconductor materials like single crystals of silicon and germanium and their chemical compositions when doped with other elements, made possible the production of the solid state transistors and other precise electronic devices, especially computers in the later stage of its scientific advancements. Since 1950s, several important discoveries in nuclear science have resulted in the synthesis of the heavy and super-heavy elements beyond uranium with sufficient stability enabling to study their properties in conformity with periodic law of the periodic table. American nuclear chemist G. T. Seaborg along with others is best known for the discovery and isolation of the trans-uranium elements. The chemical element, Seaborgium (element 106), was named in his honor during his life time like that of the chemical element, Einsteinium (element 99), named to honor Albert Einstein. Currently, several groups of nuclear scientists have been engaged in successful synthesis of the super-heavy elements in different advanced nuclear research laboratories in USA, USSR, France and Germany and the SCIENCE AND CULTURE, NOVEMBER-DECEMBER, 2016 latest evidence of their endeavor is the production and characterization of the super-heavy element, Z-117, through the nuclear reaction, 249Bk(48Ca, 3-4n)293,294Z-117, in GSI, Germany, also reported earlier by a Group of Russian scientists in 2010. In the earlier period, the chemists in general were very much reluctant in the application of mathematics in chemistry. Auguste Comte in 1830 made the comment, “Every attempt to employ mathematical methods in the study of chemical questions must be considered profoundly irrational and contrary to the spirit of chemistry”. However, in the later part of the nineteenth century, the conception has gradually been changed, for example, August Kekule wrote “I rather expect that we shall someday find a mathematico-mechanical explanation for what we now call atoms which will render an account of their properties’’. With rapid progress and outstanding development in chemical research, the activities of chemistry have now become intermingled with almost all major branches of science resulting in extensive advancement of science in general. Disciplines of Chemistry In practice, the subject of chemistry is now traditionally grouped into several major sub-disciplines based on the type or kind of matter being investigated, although there are several cross-disciplinary and more specialized fields in chemical science. Some of the major sub-disciplines of chemistry are – Analytical chemistry (deals with chemical composition and structure of sample materials), Biochemistry (deals with substances of biological organisms), Inorganic chemistry (deals with inorganic matters), Nuclear chemistry (deals with sub-atomic nuclear particles and transmutations), Organic chemistry (deals with carbon based matters), Physical chemistry (deals with the chemical processes involving physical concepts such as thermodynamics, quantum mechanics, etc.) and others. In addition, many more specialized fields such as Agro-chemistry, Atmospheric chemistry, Chemical biology, Cosmo-chemistry, Electrochemistry, Environmental chemistry, Geo-chemistry, Green chemistry, Marine chemistry, Material science, Nanotechnology, Natural product chemistry, Petro-chemistry, Pharmacology, Photochemistry, Polymer chemistry and many others, have been emerged in recent years with rapid advancement in chemical sciences. Conclusion Studies in chemistry, in early civilizations, were VOL. 82, NOS. 11–12 primarily confined to simple observations on the natural materials under the environmental conditions of temperature, pressure and exposition to natural solar radiations on Earth. Gradually, the rational reasoning on the existences of the surrounding matters in different phases started with the acceptance of the fundamental concepts and laws time to time introduced in the development of modern chemistry. In the beginning, however, the matters within the atomic nuclei or the nuclear phenomenon were disregarded. With the advancement of science, the subject of chemistry has been re-defined as the science of matter dealing with the composition and structural properties of substances and their transformations under different conditions, both natural and artificial. Discovery of radioactivity, the sub-atomic particles and studies on the atomic structure in the later period of modern chemistry encouraged the scientists to rethink about the characteristic properties of matter. Studies on matters in their atomic, molecular or aggregate scale, including the effects of interactions (bombardment) of fundamental particles like proton, neutron or heavy ions with matter are now formally recognized as essential subjects of investigation in chemistry. Presently, the advanced areas of chemical science like quantum chemistry, nuclear chemistry and many others have been extensively developed and formally accepted as important sub-fields of study in chemistry. Nevertheless, the field of chemistry is very broad and is sometimes considered as the central science as it bridges many other major branches of science and hence the claim that chemistry is everywhere is found to be true and justified. Appendix Scientists engaged in studies in chemical science are generally designated as chemists and the subject involved is known as chemistry. Some essential concepts of study in chemistry are atom, element, molecule, compound, ion, bonding, energy, etc. Matter can exist in several phases and can be studied in isolation or in combination. The most familiar phases are solid, liquid and gaseous and the less familiar phases include plasmas, Bose-Einstein condensates and fermionic condensates, and paramagnetic and ferromagnetic phases of magnetic materials. According to the International Union of Pure and Applied Chemistry (IUPAC) gold book, a chemical reaction is ‘a process that results in the inter-conversion of chemical species’. A chemical reaction can be depicted symbolically through chemical equation. The number of atoms on the 351 left and the right sides of a chemical reaction for chemical transformation is equal but when unequal, the transformation by definition is not chemical, but rather a nuclear reaction or a radioactive decay process. The standard nomenclature of a chemical compound is set by the IUPAC. The Chemical Abstracts Service has devised a method to index chemical substances. In the initiative of the IUPAC and of the United Nations Educational, Scientific, and Cultural Organization (UNESCO), the year 352 2011 was declared by the United Nations as the International Year of Chemistry. The present article is primarily based on the (i) History of Chemistry, Wikipedia, the free encyclopedia and (ii) Chemistry, Wikipedia, the free encyclopedia, retrieved on 23. 09. 2015. To have detailed information, further readings of the cited Wikipedia along with the referred references and other relevant communications are needed. S SCIENCE AND CULTURE, NOVEMBER-DECEMBER, 2016
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