THE STORY OF CHEMISTRY The story of the development of chemistry took hundreds of years until modern chemistry emerged

late in the eighteenth century. Archaeological evidence proves that the inhabitants of ancient Egypt and Mesopotamia (--- to 600 BC) were skilled in the practical crafts -the production of metals from ores, the manufacture of pottery, brewing, bakering and the preparation of medicines and dyes. They knew how to obtain copper by heating malachite ore with charcoal, but did not seek to know why their process worked. These highly developed crafts, which are chemical processes, were empirical. They were based on practical experience alone, without reference to chemical principles. The philosophical (theoretical) aspect of chemistry began in classical Greece (600 BC to 300 BC). The foundation of Greek science was the search of principles, concepts of the composition of substances and the theory about the matter. They first mentioned atoms as separate and distinct units that matter consists of. The Greeks, however, speculated much, but did not try experimentally to prove their theories. The philosophical tradition of ancient Greece and the craft tradition of ancient Egypt met in Alexandria and alchemy was the result of the union (300 BC to 1650 AD). Its aims were the transmutation of base metals into noble metal gold, the discovery of all-healing substance, and the preparation of elixir of longevity. Throughout most of the long centuries the alchemists had not carried out scientific experiments. Not earlier than the end of the seventeenth century Robert Boyle severely criticized alchemical thought emphasizing that chemical theory should be derived from experimental evidence. Later on, phlogiston theory (1650-1790) assumed phlogiston to be a constituent for combustion. The adherents of this erroneous theory had never realized the importance of weighing and measuring. The development of modern chemistry has been the trial- and-error result of the efforts of many individuals working in many different ways but sharing certain basic assumptions: that quantitative measurement is possible and that there are relationships between observable facts. The work of the French chemist, Antoine Lavoisier, in the late eighteenth century is regarded as the beginning of modern chemistry. He relied on the results of quantitative experimentation to arrive at his explanations of a number of chemical phenomena. Lavoisier stated explicitly that the total mass of all materials entering into a chemical reaction equals the total mass of all the products of the reaction. In other words, he used the law of conservation of mass as the cornerstone of his science. In his book, published in 1789, Lavoisier used essentially modern terminology. The presentday language of chemistry is based on the system of nomenclature devised by Lavoisier. In the two centuries following Lavoisier more has been learned about chemistry than in the twenty centuries preceding him. The impact of chemistry on the modern world, both its benefits and the problems it creates, is tremendous. Chemistry has gradually developed several principal branches the nature of which is indicated by their names, that is, organic, inorganic, analytical, biochemistry, nuclear, theoretical, etc. The boundaries of the various branches of science are indistinct; hence it is almost impossible to state, "this is the field of chemistry". The interests of scientific fields overlap, and the concepts and methods find universal application. Therefore, it is hard to give a concise, precise, and accurate definition of chemistry. Nevertheless, chemistry is usually defined as the science that deals with the composition, properties, and transformations of matter. Since matter is anything that occupies space and has mass,

the scope of chemistry and its impact on our everyday lives is enormous. The focus of chemistry is the chemical reaction.

SOME BASIC CHEMICAL TERMS One major goal of chemistry is to describe the properties of the many different forms of matter we encounter. Matter, the material of which the universe is composed, may be defined as anything that occupies space and has mass. A second goal facing chemists is to understand the relationship between the properties of materials and their internal structure. Most of the materials we encounter in our daily lives, such as air, milk, and steel, are mixtures. Mixtures contain two or more substances that can be physically separated from each other. Some mixtures, such as sand mixed with gravel, are heterogeneous, in other words, we would have no trouble distinguishing gravel from sand, and the mixture could be separated by a simple mechanical procedure such as sifting the sand from the gravel. Other mixtures, for example a mixture of alcohol and water are homogeneous - the mixture has the same composition throughout the entire sample and is usually called a solution. There are many different separation methods that can be used to separate such a mixture into its pure components. For example, by selective evaporation distillation. Mixtures resemble their components. A pure substance is matter that cannot be separated into other substances by physical means. Each pure substance has its own particular set of physical properties -boiling point, freezing point, melting point, density, color, and mechanical, thermal, electric, and magnetic properties. A chemical reaction transforms one or more substances into different substances. The substances that take part in the reaction are called reactants, and those that are formed by the reaction are called products. The products of a chemical reaction usually do not resemble their reactants. Chemical reactions often differ from physical processes in the way that the chemical reaction either produces or consumes a large amount of energy. Pure substances are compounds and elements. Compounds are substances that are composed of two or more elements in fixed proportions. The law of definite proportions states that a pure compound always consists of the same proportion by mass. Over ten thousand inorganic compounds are known and over one million organic compounds have been either synthesized or isolated from natural sources. The ancient Greeks originated the concept that all matter is composed of a limited number of simple substances called elements. The Greeks assumed that all terrestrial matter is derived from four elements: earth, air, fire, and water. This Greek thought dominated scientific thought for centuries. Antoine Lavoisier firmly established the concept of a chemical element as a substance that resists decomposition and cannot be synthesized. At the present time, 112 elements are known. Of these, 85 have been isolated from natural sources, and the remainder has been prepared by nuclear reactions. The most abundant element in the universe as a whole is hydrogen, which is thought to constitute about 75% of the total mass of the universe. The Earth consists of a core surrounded successively by a mantle, and a thin crust. If the entire earth were considered the most abundant element would be iron. At the end of the nineteenth century it was discovered that some of the substances classified as elements do decompose spontaneously to form other elements. Therefore, the definition of an element is changed to be a substance that cannot be decomposed, synthesized, or transformed into

another element by chemical reactions. The processes that do decompose, synthesize, or transform elements are called nuclear reactions. Nuclear reactions are easy to recognize because they either release or consume tremendous amounts of energy. Mass is the tendency of an object to resist a change in motion. The more massive an object, the harder it is to start it moving, slow it down, or change its direction once it is in motion. Unlike weight, the mass of an object does not change with its environment. A brick in a spacecraft may be 'weightless, but kicking it would be just as painful as on Earth the brick retains its mass and still resist a change in motion. The weight of an object is the force of gravity acting on it. Although weight is proportional to mass, it also depends on the environment where weight is measured.

ATOMIC THEORY Since ancient times natural philosophers were interested in the possibility that mass occurs in quanta (quantum is an indivisible unit of definite size). The atomic theory of Greek philosopher Democritus (fifth century BC) held that the subdivision of matter would ultimately yield atoms, which could not be further divided. Greek word atomos means uncut or indivisible. In the beginning of the nineteenth century the English chemist and physicist, John Dalton, went further and made the atomic theory quantitative by showing that it is possible to determine the relative masses of the atoms of different elements. Dalton's atomic theory gave a simple explanation of the previously formulated law of conservation of mass and the law of definite proportions. Since the time of Dalton's formulation, this theory has been modified to explain later observations, such as the variations in the composition of a compound. The present form of the atomic theory contains the following hypotheses: - All matter consists of small particles called atoms. - Atoms cannot be chemically synthesized, decomposed, or transformed into another type of atoms. - All atoms of a particular element are identical in those properties that influence chemical behaviour. - Atoms can chemically react to form clusters of atoms called molecules. All molecules of a particular compound are identical in terms of the type, number, and geometrical arrangement of the constituent atoms. - A chemical reaction is a change in molecular structure. One hypothesis of Dalton's original theory, that all atoms of a particular element have the same mass, which would mean that a compound's composition could never vary, has been rejected in view of the more recent evidence. Since Dalton's time it has been discovered that atoms of the same element can differ in mass. Atoms of the same element with different masses are called isotopes. On the basis of his theory, Dalton proposed a third law, the law of multiple proportions. This law follows from Dalton's view that the atoms in a compound are combined in a fixed proportion. If two elements form two compounds, the atom ratio of the compounds must be different. Since these atomic ratios are simple whole-number (integer) values, the relationship between the atom ratios of

the two compounds is also a simple whole-number ratio. The experimental verification of the law of multiple proportions was strong support of Dalton's theory. Heat is the energy of molecular motion. The various sorts of molecular motion -vibration, rotation, and movement through space - are major factors governing the physical behavior and chemical properties of a sample. In describing molecular motion, many ideas and definitions of Newton's classical physics are used, in particular the terms mass, force, and momentum. A force is any influence that alters the speed or direction of an object. Until it encounters a force, an object at rest remains at rest, and a body in motion continues to move in a straight line at constant speed (Newton's first law of motion). Force is measured in units called newtons, each newton being equal to 1 kgm/s2. Two forces of equal size pulling in opposite directions cancel each other's effect so that the object experiences no net force. An important property of moving objects, significant for the behavior of the constituent parts of atoms, is momentum - the mass of an object (m) multiplied by its velocity (v). When a moving billiard ball collides with another billiard ball at rest, the moving ball slows down and loses momentum while the stationary object picks up speed and gains momentum. Momentum can be transferred from one object to another, but it is never created or destroyed. The statement of this phenomenon is called the law of conservation of momentum. Whenever a force moves an object through a distance, it performs work on the object. Work is measured in units called joules (J). Energy is ability to do the work. There are two types of mechanical energy. An object possesses kinetic energy due to its own motion, and derives its potential energy from its position and the forces acting on it. A weight suspended on a wire 3 m above the floor has more energy than when it rests on the floor. Should the wire snap, the weight will fall and gain kinetic energy as it speeds up. Energy is also measured in joules. The law of conservation of energy says that the total energy in the universe remains constant. One object may yield energy to another, potential energy may change to kinetic energy or light, but no creation or destruction of energy occurs. Heat is the kinetic energy of the molecules in a sample. Temperature is a measure of the intensity of heat in a sample and is independent of the size of the sample.

STOICHIOMETRY Stoichiometry is the branch of chemistry that deals with the quantitative relationships between elements and compounds in chemical reactions. Greek 'stoicheion' means element and 'metron' means measure. Stoichiometric calculations are the basic operations of chemistry - without them it would be impossible to analyze mixtures, design economical methods for synthesizing the products that are essential to technology, or to develop the theoretical tools needed to understand the nature of atoms and molecules. For measuring the masses of atoms, a unit system atomic mass {atomic weight) has been introduced. Atomic mass unit (abbreviated u) is based on an arbitrarily chosen standard mass. The standard for the atomic mass scale is a single atom of the most abundant isotope of carbon, known as 12 C. By common agreement, an atom of this isotope has a mass of exactly 12 u, so that 1 u is 1/12 the

mass of the 12C isotope. The mass of any other atom can be measured in atomic mass units. Having in mind the existence of isotopes, 'average' atomic masses are more useful in chemistry than the individual atomic masses of the isotopes. Periodic tables usually list the average atomic masses (atomic weights) of the elements. The molecular mass {molecular weight) of a substance is the sum of the masses of the atoms that make up one of its molecules. A molecular formula represents the number of atoms of each element in a molecule. We write the chemical symbol for each element present in the substance and the number of atoms of that element per molecule by a subscript number at the lower right of the symbol. The absence of a subscript means that only one atom is present per molecule. For example, the molecular formula for the vitamin niacin is C6H5NO2 - each niacin molecule contains six carbon atoms, five hydrogen atoms, a single nitrogen atom, and two oxygen atoms. To determine the molecular formula of a compound, it is necessary to know both its molecular mass and percentage composition. The simplest formula (also called the empirical formula) of a compound is the simplest whole-number ratio of atoms that is consistent with its composition. It is used in place of molecular formula when the information about molecular mass is lacking. Many compounds have well defined simplest formulas but no definable molecular formula. For instance, SiO2 is the simplest formula of a compound containing various numbers of oxygen and silicon atoms present in a 2:1 ratio. Every sample of the compound contains a range of molecular sizes. Rather than write an incompletely defined formula such as SixO2x, we write SiO2, with the understanding that this formula does not necessarily represent the molecular formula. Chemists recognize certain molecular and simplest formulas by experience and by theoretical knowledge about the nature of the chemical bonds in a substance. A sample of any element that has a mass in grams numerically equal to the atomic weight of the element contains the same number of atoms. This number is called Avogadros number, named after Antonio Avogadro who first interpreted the behavior of gases in terms of the number of reacting atoms. The value of Avogadro's number was experimentally determined to be 6.022 1023. The amount of a substance that contains Avogadro's number of elementary units is called a mole (abbreviated mol). Chemical equations are representations of reactions with the symbols and formulas of the elements and compounds involved. The reactants are indicated on the left and the products on the right. An arrow may be used instead of the customary equal sign of the algebraic equation; it may be considered as an abbreviation for the word 'yields'. The first step in writing a chemical equation is to ascertain the products of the reaction in question. Carbon disulphide, CS2, reacts with chlorine, Cl2, to produce carbon tetrachloride, CCl4, and disulphur dichloride, S2Cl2. To represent this we write CS2 + C12 CC14 + S2C12 This equation is not quantitatively correct because it violates the law of conservation of mass. This is an unbalanced equation. The number of atoms of each element must be the same on both sides of the equation. The equation can be balanced by indicating that three molecules of chlorine should be used for the reaction. Thus,

CS2 + 3C12 CC14 + S2C12 is a balanced equation. Balanced equations display the relationships between the number of moles of each reactant and product in the reaction, and these relationships allow us to compute mass relationships between reactants and products. Suppose, for example, that we are asked how much H2O can be prepared from 2 mol of H2 and 2 mol of O2. More O2 has been supplied than can be used. When all the H2 has been consumed, the reaction will stop. One mole of O2 will remain unreacted. The amount of H2 limits the reaction. Hydrogen, therefore, is called the limiting reactant. The percent yield is the ratio, expressed in percents, of the actual yield to the theoretical yield. Theoretical yield is predicted by stoichiometry using a limiting reactant calculation.

THE PERIODIC CLASSIFICATION OF THE ELEMENTS The amount of information now available on the chemical properties and reactions of the pure substances is, considering the limitations of human mind, essentially infinite. No present-day chemist can hope to be familiar with all the chemistry of all the pure substances. Each year the volume of information published in the chemical journals far exceeds the reading capacity of any individual. Much of this information is in very specialized areas and requires extensive reading of the previous literature before it can be understood. However, there are generalizations that can be used to classify and predict the chemical and physical properties of pure substances. If the first 25 elements are listed in order of their atomic weights, even a casual inspection reveals that there is regularity in the physical properties of the elements - density of solid, melting point, and boiling point. Especially ionization energy shows the most striking periodic, or cyclic character. There are also generalization and regularities in the chemical properties of the above said elements. Many of these elements form both chlorides and oxides and the cycles of these compounds are perfectly regular. If the physical properties of the chlorides, or other binary compounds, of these elements are investigated, the same periodicity of similar properties is found that is observed for the elements themselves. An extensive study of all the elements shows the existence, though somewhat less simple, of periodicity of their chemical and physical properties. All the conclusions are summarized as the Periodic Law: The elements, if arranged in order of their atomic weights, exhibit an evident periodicity of properties. Several early chemists suspected the existence of the regulations among the elements, but at that time they had no evidences and the idea seemed so impossible that they paid to it very little attention. Between 1869 and 1871 D.I. Mendeleev, a brilliant, young Russian chemist, wrote a series of papers on the periodic properties of the elements. He was very sure of his conclusions so that he boldly asserted that gaps in his arrangements corresponded to the elements yet to be discovered. By noting the positions of the gaps, Mendeleev was able to predict many of the properties of the missing

elements. Gallium, scandium, and germanium were among the elements predicted by Mendeleev, and they were discovered in later years. The agreement of the actual properties of the three elements with the properties predicted by Mendeleev was truly remarkable. The success of predictions made by Mendeleev removed any doubt of the validity of the concept of the property periodicity. It explains the association of Mendeleev's name with the periodic law and periodic table. The horizontal rows of the periodic table are called periods and the vertical columns are called groups. Elements in the same group have closely related physical and chemical properties. The elements on the left side and in the center of the periodic table are metals. They have characteristic properties called metallic properties - high electric and thermal conductivity, metallic luster, the ability to be hammered into sheets (malleability) and to be drawn into wires (ductility). The elements on the right side of the periodic table are nonmetals; they have not metallic properties. The metallic properties are most pronounced for the elements in the lower left corner of the periodic table, and the nonmetallic properties are most pronounced for the elements in the upper right corner. The transition from metals to nonmetals is marked by the elements that occupy a diagonal region. These elements are called metalloids. The groups are marked by numbers and in addition are given the following descriptive names: noble gases, alkali metals, alkaline-earth metals, boron or aluminum group, carbon and silicon group, nitrogen or phosphorous group, oxygen group, halogen group, etc. The periodic table is a most useful tool for the organization of chemical knowledge. The fact that the chemical and physical properties of the elements are correlated makes possible the prediction of many chemical facts on the basis of a relatively small amount of information.

ATOMIC STRUCTURE Basic to any theory of matter is a conception of its structure. The notion that matter ultimately consists of discrete particles is a very old one. About 400 BC this idea was put forward in the writings of Democritus, a Greek philosopher. Later, the idea that matter is particle in nature was based mainly on the intuition of adherents to this theory. In the beginning of the nineteenth century an English chemist, John Dalton, placed this idea on a firm experimental basis and stated that all substances consist of small particles of matter of a number of different kinds, corresponding to the different elements. He called these particles 'atoms', from the Greek word 'atomos', meaning indivisible. The atomic theory gave a simple explanation of the previously formulated quantitative laws of chemistry. However, Dalton's concept of a structureless atom provided no mechanism to explain new observations and a conclusion that atom is electrical in nature. The spontaneous disintegration of naturally radioactive atoms into smaller particles contradicts the Daltonian hypothesis that atoms are unalterable. These discoveries introduced a more complete theory of the structure of atoms, the nuclear theory of the atom, and reaffirmed the atom as the unit of chemical changes. On the basis of Faraday's work, George Stoney concluded that units of electrical charge were associated with atoms and in 1891 Stoney suggested that these units be called electrons. ('Electron' means in Greek 'amber'). Amber is electrified when rubbed with wool. Attempts to pass an electric current through a vacuum led to the discovery of cathode rays. In the latter part of the nineteenth century cathode rays were extensively studied. The results of many scientists led to the conclusion that the rays are streams of fast moving, negatively charged particles, eventually called electrons.

Both the mass and the radius of an electron are extremely small. Its radius cannot be determined exactly; it is somewhat of the order of 10-12 cm. Its mass was found to be about 1/1838 of the mass of the hydrogen atom. The most important property of the electron is its electric charge. Each electron carries the same amount of charge. The magnitude of the charge, which is negative, is 1.602210-19 C. This charge is called the unit electric charge. The electric current is the result of the flow of electrons through a metal. The atomic number of an element is equal to the number of electrons surrounding its atomic nucleus. All atoms contain the same number of electrons. All hydrogen atoms contain one electron; all atoms of the element copper contain 29 electrons. Electrons are found in the outer regions of atoms, forming a negative charge cloud about the atomic center. Nucleus, located at the center of the atom, has a diameter ten thousand times smaller than the diameter of the atom itself. Its mass is very nearly equal to that of the atom. It carries a positive charge, equal and opposite to the total negative charge of the electrons in the atom, making the atom electrically neutral. There are two types of constituent particles in a nucleus, protons and neutrons. A proton has a unit of positive charge +1 and a mass of approximately 1 u. In 1911 Ernest Rutherford performed a series of experiments using a radioactive source and letting a beam of high-energy particles (He2+ ions) fall on a piece of thin gold foil. Most of the particles passed directly through the foil, thus proving that most of the volume of an atom is empty space. Since atoms are electrically neutral, a given atom must contain as many electrons as protons. In 1920 Rutherford postulated the existence of an uncharged particle. Since this particle is uncharged it is difficult to detect. In 1932, however, James Chadwick published the results of his work that established the existence of the neutron from data on certain nuclear reactions in which neutrons are produced. It has been discovered that nuclei of atoms of the same element may differ in mass. The number of protons in a nucleus equals the atomic number and is the same for all atoms of an element. The mass number of an atom is the sum of the protons and neutrons in its nucleus. Isotopes have the same number of protons but different number of neutrons present in the nuclei. For example, two different kinds of hydrogen atoms are found in nature, the 1H (protium) nucleus is a proton, and the 2H (deuterium) nucleus contains a neutron and a proton, each of which contribute approximately 1 u to the mass of the atom. The sum of the protons and neutrons in a nucleus is called the 'mass number' of an atom. When we wish to identify a certain isotope, we display its mass number at the upper left of the chemical symbol. Thus, the symbol 94Zr2+ stands for an atom with an atomic number 40 and a mass number 94. Its 2+ charge means that there are two fewer electrons than protons in this ion. The instrument, mass spectrograph measures the charge-to-mass ratio of atomic particles, i.e. measures the magnetic deflections of ions, giving information about the masses and abundances of isotopes. QUANTUM MECHANICS The early twentieth century witnessed a fundamental revolution with regard to the explanation of natural phenomena. Scientists developed an entirely new physics to describe the word of the atom. This revolution allowed scientists to reexamine their fundamental hypotheses, and by doing so, they were able to see previously unsuspected relationships between such diverse phenomena as light and

chemical behavior. To develop the current ideas about atomic and molecular structures, chemists used the idea of the new theory called quantum mechanics. Light is a unique form of energy that can travel through empty space and matter. All varieties of light - for example, visible light of various colors, the infrared light emitted by hot objects, and the highly penetrating ultraviolet light - travel through a vacuum at a constant velocity, Co = 3.00108 m/s, and can change into other energy forms upon contact with matter. Because light exhibits interference phenomena such as diffraction, it can be regarded as a wave phenomenon. Each form of light has a characteristic wavelength (the distance from crest to crest, or trough to trough, usually measured in nanometers, nm), amplitude, and frequency v (the number of waves that pass a given spot in a second, measured in hertz, Hz). The various forms of light differ in their wavelengths and frequencies. In a vacuum, = Co/ v. The wave model explaining the diffraction of light seemed complete. However, in the beginning of the twentieth century there were accumulated experimental evidences that could not be explained by the wave model. This led to the revival of the belief of Newton's followers that light beam is a stream of small particles. In 1900, Max Planck suggested that radiant energy could be absorbed or given off only in definite quantities, called quanta. In 1905, Albert Einstein proposed that Planck's quanta are discrete bits of energy, later named photons. Planck's law states that the energy of each photon is proportional to the frequency of the light and is given by the equation Ephoton = hv, where h is a universal constant, called Planck's constant. The photon model describes some important aspects of light, but it cannot explain diffraction and other interference phenomena. Because of its limited application, the photon model supplements rather than displaces the wave model. Hot gases emit light of characteristic and precisely defined frequencies. Atomic emission spectroscopy is a current method for routine chemical analysis, which is based on that fact. For example, it is even used to learn which elements are present in stars. Niels Bohr explained the emission spectrum of hydrogen in a way that changed the foundations of physical science by making the radical assumption that the motion of an electron in an atom is quantized. The main obstacle to our understanding of the properties of chemical substances in terms of the electrons and nuclei is that small particles, like atoms, molecules, nuclei, and particularly electrons, appear to obey different laws, regarding energy and motion, than do larger bodies around us, like an automobile or a ball. Such large systems, with masses many times those of atoms, follow exactly the laws of motion first formulated by Isaac Newton, called classical mechanics. Bohr proposed that it does not apply at the atomic level, and he replaced it with the idea that an electron in an atom is restricted to discrete orbits, or energy levels. The Bohr theory explained the emission spectrum of hydrogen by assuming that the electron in the atom was restricted to one of a set of discrete, precisely defined energy levels. A hydrogen atom emits a photon corresponding to a particular emission line when its electron falls from a higher energy level to a lower. According to quantum mechanics there is a fundamental problem of observing small particles. The more precisely we determine a particle's position, the more we disturb its motion. This is the

basis of the Heisenberg uncertainty principle, which states that it is impossible to determine both the position and momentum of an electron with absolute precision. The more precisely we determine the position, the less we know about the motion, and vice versa. The electrons in an atom are moving around the atomic nucleus in approximately concentric spherical layers called electron shells. Electrons having similar energies comprise a shell and are said to be in the same energy level. The position of the electrons may be visualized as an electron cloud about the nucleus. The mathematics of wave mechanics shows that the energy state of an electron in an atom may be described by a set of four numbers, called quantum numbers. The principal quantum number, symbolized by n, indicates the average distances of the electron from the nucleus of the atom. It is a positive whole number, having values 1, 2, 3, and so on, sometimes referred to as K, L, M, N, O, and P shells. The orbital quantum number indicates the shape of the orbit in which an electron moves. They are listed in order of ascending energies designated as s, p, d, and f. The magnetic quantum number indicates the position about the three axes in space of the orbital. The spin quantum number refers to the two possibilities for spin - clockwise and counterclockwise.

ELECTRONS IN ATOMS What are line spectra? Glowing body (or actually, any body whose temperature is above 0 K) emits and absorbs radiation of all wavelengths in a continuous spectrum. In striking contrast is the spectrum of light produced when certain substances are volatilized in a flame, or when an electric discharge is passed through a tube containing gaseous atoms of an element. The light emitted by such sources consists entirely of discrete wavelengths. This kind of emission is known as a discrete spectrum or line spectrum (the lines that appear on photographic images of the spectrum are really images of the slit through which the light passes before being dispersed by the prism in the spectrograph). Every element has its own line spectrum that serves as a sensitive and useful tool for detecting the presence and relative abundance of the element, not only in terrestrial samples but also in stars. (As a matter of fact, the element helium was discovered in the sun, through its line spectrum, before it had been found on Earth.) In some elements, most of the energy in the visible part of the emission spectrum is concentrated into just a few lines, giving their light characteristic colors: yellow-orange for sodium, blue-green for mercury (these are commonly seen in street lights) and orange for neon. Line spectra were well known early in the 19th century, and were widely used for the analysis of ores and metals. The German spectroscopist R.W. Bunsen, now famous for his gas burner, was then best known for discovering two new elements, rubidium and cesium, from the line spectrum he obtained from samples of mineral spring waters. How are line spectra organized?

Until 1885, line spectra were little more than fingerprints of the elements, extremely useful in themselves, but incapable of revealing any more than the identify of the individual atoms from which they arise. In that year a Swiss schoolteacher named Balmer published a formula that related the wavelengths of the four known lines in the emission spectrum of hydrogen in a simple way. Balmers formula was not based on theory; it was probably a case of cut-and-try, but it worked: he was able to predict the wavelength of a fifth, yet-to-be discovered emission line of hydrogen, and as spectroscopic and astronomical techniques improved (the only way of observing highly excited hydrogen atoms at the time was to observe the solar spectrum during an eclipse), a total of 35 lines were discovered. These series, which span the wavelength region from the ultraviolet through infrared, are named after their discoverers (Lyman, Balmer, Paschen, Brackett, Pfund). Attempts to adapt Balmers formula to describe the spectra of atoms other than hydrogen generally failed, although certain lines of some of the spectra seemed to fit this same scheme. What were the problems with the planetary model of the atom? Rutherfords demonstration that the mass and the positive charge of the atom is mostly concentrated in a very tiny region called the nucleus forced the question of just how the electrons are disposed outside the nucleus. By analogy with the solar system, a planetary model was suggested: if the electrons were orbiting the nucleus, there would be a centrifugal force that could oppose the electrostatic attraction and thus keep the electrons from falling into the nucleus. This of course is similar to the way in which the centrifugal force produced by an orbiting planet exactly balances the force due to its gravitational attraction to the sun. This model suffers from one fatal weakness: electrons, unlike planets, are electrically charged. An electric charge revolving in an orbit is continually undergoing a change of direction, that is, acceleration. It has been well known since the time of Hertz that an accelerating electric charge radiates energy. We would therefore expect all atoms to act as miniature radio stations. Even worse, conservation of energy requires that any energy that is radiated must be at the expense of the kinetic energy of the orbital motion of the electron. Thus the electron would slow down, reducing the centrifugal force and allowing the electron to spiral closer and closer to the nucleus, eventually falling into it. In short, no atom that operates according to the planetary model would last long enough for us to talk about it. As if this were not enough, the planetary model was totally unable to explain any of the observed properties of atoms, including their line spectra. How did Bohrs theory save the planetary model... for a while? Niels Bohr was born in the same year (1885) that Balmer published his formula for the line spectrum of hydrogen. Beginning in 1913, the brilliant Danish physicist published a series of papers that would ultimately derive Balmers formula from first principles. Bohrs first task was to explain why the orbiting electron does not radiate energy as it moves around the nucleus. This energy loss, if it were to occur at all, would do so gradually and smoothly. But Planck had shown that black body radiation could only be explained if energy changes were limited to jumps instead of gradual changes. If this were a universal characteristic of energy that is, if all energy changes were quantized, then very small changes in energy would be impossible, so that the electron would in effect be locked in to its orbit. From this, Bohr went on to propose that there are certain stable orbits in which the electron can exist without radiating and thus without falling into a death spiral. This supposition was a daring one at the time because it was inconsistent with classical physics, and the theory which would eventually lend it support would not come along until the work of de Broglie and Heisenberg more than ten years later. Since Plancks quanta came in multiples of h, Bohr restricted his allowed orbits to those in which the product of the radius r and the momentum of the electron mv. Each orbit

corresponds to a different energy, with the electron normally occupying the one having the lowest energy, which would be the innermost orbit of the hydrogen atom. Taking the lead from Einsteins explanation of the photoelectric effect, Bohr assumed that each spectral line emitted by an atom that has been excited by absorption of energy from an electrical discharge or a flame represents a change in energy lost when the electron falls from a higher orbit (value of n) into a lower one. What were the main problems with Bohrs theory? There were two kinds of difficulties. First, there was the practical limitation that it only works for atoms that have one electron-- that is, for H, He+, Li2+, etc. The second problem was that Bohr was unable to provide any theoretical justification for his assumption that electrons in orbits would not lose energy by radiation. This reflects the fundamental underlying difficulty: because de Broglies picture of matter waves would not come until a decade later, Bohr had to regard the electron as a classical particle traversing a definite orbital path. How did the wave picture of the electron save Bohrs theory? Once it became apparent that the electron must have a wavelike character, things began to fall into place. The possible states of an electron confined to a fixed space are in many ways analogous to the allowed states of a vibrating guitar string. These states are described as standing waves that must possess integral numbers of nodes. The states of vibration of the string are described by a series of integral numbers n = 1,2... which we call the fundamental, first overtone, second overtone, etc. Each mode of vibration contains one more complete wave than the one below it. In exactly the same way, the mathematical function that defines the probability of finding the electron at any given location within a confined space possesses n peaks and corresponds to states in which the energy is proportional to n2. If the electron cannot be localized, can it be moving? In its lowest state in the hydrogen atom (in which l=0) the electron has zero angular momentum, so electrons in s orbitals are not in motion. In orbitals for which l>0 the electron does have an effective angular momentum, and since the electron also has a definite rest mass me = 9.111031 kg, it must possess an effective velocity. Its value can be estimated from the Uncertainty Principle; if the volume in which the electron is confined is about 1010 m, then the uncertainty in its momentum is at least h/1010 = 6.61024 kgms1, which implies a velocity of around 107 ms1 - almost one-tenth the velocity of light. The stronger the electrostatic force of attraction by the nucleus, the faster the effective electron velocity. In fact, the innermost electrons of the heavier elements have effective velocities so high that relativistic effects set in; that is, the effective mass of the electron significantly exceeds its rest mass. This has direct chemical effects; it is the cause, for example, of the low melting point of metallic mercury and of the color of gold. Why does the electron not fall into the nucleus? The negatively charged electron is attracted to the positive charge of the nucleus. What prevents it from falling in? This question can be answered in various ways at various levels. All start with the statement that the electron, being a quantum particle, has a dual character and cannot be treated solely by the laws of Newtonian mechanics. We saw above that in its wavelike guise, the electron exists as a standing wave that must circle the nucleus at a sufficient distance to allow at least one wavelength to fit on its circumference. This means that the smaller the radius of the circle, the shorter must be the

wavelength of the electron, and thus the higher the energy. Thus it ends up costing the electron energy if it gets too close to the nucleus. The normal orbital radius represents the balance between the electrostatic force trying to pull the electron in, and what we might call the confinement energy that opposes the electrostatic energy. This confinement energy can be related to both the particle and wave character of the electron. If the electron as a particle were to approach the nucleus, the uncertainty in its position would become so small (owing to the very small volume of the nucleus) that the momentum, and therefore the energy, would have to become very large. The electron would, in effect, be kicked out of the nuclear region by the confinement energy. The standing-wave patterns of an electron in a box can be calculated quite easily. What is electron spin? Each electron in an atom has associated with it a magnetic field whose direction is quantized; there are only two possible values that point in opposite directions. We usually refer to these as up and down, but the actual directions are parallel and antiparallel to the local magnetic field associated with the orbital motion of the electron. The term spin implies that this magnetic moment is produced by the electron charge as the electron rotates about its own axis. Electron spin has no classical counterpart; the magnetic moment is a consequence of relativistic shifts in local space and time due to the high effective velocity of the electron in the atom. P.A.M. Dirac predicted this effect theoretically in 1928.