JOHN DALTON (1766-1844)

1801 England

‘The total pressure of a mixture of gases is the sum of the partial pressures exerted by each of the gases in the mixture’

Partial pressures of gases:
Dalton stated that the pressure of a mixture of gases is equal to the sum of the pressures of the gases in the mixture. On heating gases they expand and he realised that each gas acts independently of the other.

Each gas in a mixture of gases exerts a pressure, which is equal to the pressure it would exert if it were present alone in the container; this pressure is called partial pressure.

Dalton’s law of partial pressures contributed to the development of the kinetic theory of gases.

His meteorological observations confirmed the cause of rain to be a fall in temperature, not pressure and he discovered the ‘dew point’ and that the behaviour of water vapour is consistent with that of other gases.

He showed that a gas could dissolve in water or diffuse through solid objects.

Graph demonstrating the varying solubility of gases

The varying solubility of gases

Further to this, his experiments on determining the solubility of gases in water, which, unexpectedly for Dalton, showed that each gas differed in its solubility, led him to speculate that perhaps the gases were composed of different ‘atoms’, or indivisible particles, which each had different masses.
On further examination of his thesis, he realised that not only would it explain the different solubility of gases in water, but would also account for the ‘conservation of mass’ observed during chemical reactions – as well as the combinations into which elements apparently entered when forming compounds – because the atoms were simply ‘rearranging’ themselves and not being created or destroyed.

In his experiments, he observed that pure oxygen will not absorb as much water vapour as pure nitrogen – his conclusion was that oxygen atoms were bigger and heavier than nitrogen atoms.

‘ Why does not water admit its bulk of every kind of gas alike? …. I am nearly persuaded that the circumstance depends on the weight and number of the ultimate particles of the several gases ’

In a paper read to the Manchester Society on 21 October 1803, Dalton went further,

‘ An inquiry into the relative weight of the ultimate particles of bodies is a subject as far as I know, entirely new; I have lately been prosecuting this enquiry with remarkable success ’

Dalton described how he had arrived at different weights for the basic units of each elemental gas – in other words the weight of their atoms, or atomic weight.

Dalton had noticed that when elements combine to make a compound, they always did so in fixed proportions and went on to argue that the atoms of each element combined to make compounds in very simple ratios, and so the weight of each atom could be worked out by the weight of each element involved in a compound – the idea of the Law of Multiple Proportions.

When oxygen and hydrogen combined to make water, 8 grammes of oxygen was used for every 1 gramme of hydrogen. If oxygen consisted of large numbers of identical oxygen atoms and hydrogen large numbers of hydrogen atoms, all identical, and the formation of water from oxygen and hydrogen involved the two kinds of atoms colliding and sticking to make large numbers of particles of water (molecules) – then as water has an identity as distinctive as either hydrogen or oxygen, it followed that water molecules are all identical, made of a fixed number of oxygen atoms and a fixed number of hydrogen atoms.

Dalton realised that hydrogen was the lightest gas, and so he assigned it an atomic weight of 1. Because of the weight of oxygen that combined with hydrogen in water, he first assigned oxygen an atomic weight of 8.

There was a basic flaw in Dalton’s method, because he did not realise that atoms of the same element can combine. He assumed that a compound of atoms, a molecule, had only one atom of each element. It was not until Italian scientist AMADEO AVOGADRO’s idea of using molecular proportions was introduced that he would be able to calculate atomic weights correctly.

In his book of 1808, ‘A New System of Chemical Philosophy’ he summarised his beliefs based on key principles: atoms of the same element are identical; distinct elements have distinct atoms; atoms are neither created nor destroyed; everything is made up of atoms; a chemical change is simply the reshuffling of atoms; and compounds are made up of atoms from the relevant elements. He published a table of known atoms and their weights, (although some of these were slightly wrong), based on hydrogen having a mass of one.

Nevertheless, the basic idea of Dalton’s atomic theory – that each element has its own unique sized atoms – has proved to be resoundingly correct.

If oxygen atoms all had a certain weight which is unique to oxygen and hydrogen atoms all had a certain weight that was unique to hydrogen, then a fixed number of oxygen atoms and a fixed number of hydrogen atoms combined to form a fixed weight of water molecules. Each water molecule must therefore contain the same weight of oxygen atoms relative to hydrogen atoms.

Here then is the reason for the ‘law of fixed proportions’. It is irrelevant how much water is involved – the same factors always hold – the oxygen atoms in a single water molecule weigh 8 times as much as the hydrogen atoms.

Dalton wrongly assumed that elements would combine in one-to-one ratios as a base principle, only converting into ‘multiple proportions’ (for example from carbon monoxide, CO, to carbon dioxide, CO2) under certain conditions. Each water molecule (H2O) actually contains two atoms of hydrogen and one atom of oxygen. An oxygen atom is actually 16 times as heavy as a hydrogen atom. This does not affect Dalton’s reasoning.

The law of fixed proportions holds because a compound consists of a large number of identical molecules, each made of a fixed number of atoms of each component element.

Although the debate over the validity of Dalton’s thesis continued for decades, the foundation for the study of modern atomic theory had been laid and with ongoing refinement was gradually accepted.

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JOHN DALTON

1808 – Manchester, England

‘All matter is made up of atoms, which cannot be created, destroyed or divided. Atoms of one element are identical but different from those of other elements. All chemical change is the result of combination or separation of atoms’

Dalton struggled to accept the theory of GAY-LUSSAC because he believed, as a base case, that gases would seek to combine in a one atom to one atom ratio (hence he believed the formula of water to be HO not H2O). Anything else would contradict Dalton’s theory on the indivisibility of the atom, which he was not prepared to accept.

The reason for the confusion was that at the time the idea of the molecule was not understood.
Dalton believed that in nature all elementary gases consisted of indivisible atoms, which is true for example of the inert gases. The other gases, however, exist in their simplest form in combinations of atoms called molecules. In the case of hydrogen and oxygen, for example, their molecules are made up of two atoms, described as H2 and O2 respectively.

Gay-Lussac examined various substances in which two elements form more than one type of compound and concluded that if two elements A and B combine to form more than one compound, the different masses of A that combine with a fixed mass of B are in a simple whole number ratio. This is the law of multiple proportions.

AVOGADRO’s comprehension of molecules helped to reconcile Gay-Lussac’s ratios with Dalton’s theories on the atom.

Gay-Lussac’s ratio for water could be explained by two molecules of hydrogen (four ‘atoms’) combining with one molecule of oxygen (two ‘atoms’) to result in two molecules of water (2H2O).

2H2 + O2 ↔ 2H2O

When Dalton had considered water, he could not understand how one atom of hydrogen could divide itself (thereby undermining his indivisibility of the atom theory) to form two particles of water. The answer proposed by Avogadro was that oxygen existed in molecules of two and therefore the atom did not divide itself at all.

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WILLIAM PROUT (1785-1850)

1815 – UK

‘Atoms are not the smallest thing’

After ANTOINE LAVOISIER had compiled his list of the then known elements, another 32 were added in the years following his death. Fifty kinds of fundamental building blocks for matter seemed excessive. In 1815 Prout, using AVOGADRO’s method of comparing the relative densities and weights of gases, proposed that all atoms appeared to have weights that were exact multiples of the weight of the lightest atom, hydrogen, and that the different atomic weights of elements are whole-number multiples of the atomic weight of hydrogen (Prout’s hypothesis).

Portreait of William Prout (c) The University of Edinburgh Fine Art Collection; Supplied by The Public Catalogue Foundation

WILLIAM PROUT

He took this as proof that all atoms were actually made from hydrogen atoms and the idea was adopted as atomic theory and used for later investigations of atomic weights and the classification of the elements.

If all atoms are made from atoms of hydrogen, then it could be possible to transform an atom of one element into an atom of another.
If atoms had been assembled from other things, then they themselves could not be the smallest things in creation.

Apart from the method of weighing atoms being controversial, there are exceptions to the rule. Chlorine is 35.5 times as heavy as hydrogen.

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SIR JOHN JOSEPH THOMSON (1856-1940)

1897 – England

’Not only was matter composed of particles not visible even with the modern microscope, as scientists from DEMOCRITUS to DALTON had surmised, but those particles were themselves composed of even smaller components’

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JJ THOMSON

By the end of the nineteenth century scientists had cleared up much of the confusion surrounding atomic theory. The discovery of the sub-atomic particle was made in April 1897. They believed that they now largely understood the properties and sizes of the atoms of elements; without question, hydrogen was the smallest of all.

When JJ Thomson announced the discovery of a particle one thousandth the mass of the hydrogen atom the particles were named ‘electrons’ and have been a fundamental part of the understanding of atomic science ever since.

Thomson was investigating the properties of cathode rays, now known to be a simple stream of electrons, but at the time the cause of widespread debate. The rays were known to be visible, like normal light, but they were quite clearly not normal light. He devised a series of experiments, which would apply measurements to the cathode rays and clarify their nature. The rays were created by passing an electric charge through an airless or gasless discharge tube.

By improving the vacuüm in the tube, it was demonstrated that the rays could be deflected by electric and magnetic fields. Thomson drilled a hole in the anode of the tube to allow the mysterious rays from the cathode to pass through. In the space after the anode, he arranged that a magnetic force field from a magnet would tug the cathode rays in one direction, and an electric force field between two electrically charged metal plates would tug them in the opposite direction. The rays would eventually strike the glass wall of the tube to create a familiar greenish spot of light on the phosphor-coated tube.

Thomson concluded that the rays were made up of particles, not waves. He saw that the properties of the particles were negative in charge and didn’t seem to be specific to any one element; they were the same regardless of the gas used to transport the electric discharge, or the metal used at the cathode. From his findings he concluded that cathode rays were made up of a jet of ‘corpuscles’ and, more importantly, that these corpuscles were present in all elements. Thomson devised a method of measuring the mass of the particles and found them to be a fraction of the weight of the hydrogen atom.

The position of the spot indicated how much the beam of cathode rays had been deflected. The deflection could be made zero by adjusting the magnetic and electric forces so that they perfectly balanced. In such a situation, Thomson could read off the strength of the electric force. He knew in theory how the magnetic force on a charged particle depends on its speed. By equating the two forces, he was able to deduce the speed of the cathode rays. The deflection was also influenced by the electric charge carried by the cathode ray particles, and their mass. The larger the charge, the greater the force the particles felt and the greater their deflection, the smaller the mass, the easier it was for any force to push the particles about and again, the greater their deflection.

Independent evidence from electrolysis (passing electricity through liquids) that electric charge came in discreet chunks, which he assumed to be carried by individual cathode ray particles, enabled Thomson to calculate their mass.
He arrived at a figure that was a thousand billion billion billionth of a kilogram – a 1000th of the mass of a hydrogen atom.

Knowing the deflection of the dot and the velocity of the particles (the slower the particles, the longer they were exposed to the electric force and the greater the deflection of the glowing dot), Thomson expected to be able to deduce their charge and mass. What he actually deduced was a combination of their charge and mass.

Atoms were made of smaller things, but the fundamental building-blocks were not hydrogen atoms, as had been maintained by PROUT.

Thomson’s particles were christened ‘electrons’ and were the first subatomic entities. Thomson visualized a multitude of tiny electrons embedded ‘like raisins in a plum pudding’ in a diffuse ball of positive charge.

‘The atom is a sphere of positively charged protons in which negatively charged electrons are embedded in just sufficient quantity to neutralise the positive charge’

This was the accepted picture of the atom at the start of the twentieth century until RUTHERFORD found a way to probe inside the atom in 1911.

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ANTOINE-HENRI BECQUEREL (1852-1908)

1898 – France

BECQUEREL

BECQUEREL

‘1903 – Awarded the Nobel-Prize for Physics jointly with Marie and Pierre Curie’

picture of a rock displaying fluorescence under short wavelength radiation

The phenomenon of fluorescence – displayed under short wavelength radiation

Stimulated by WILHELM CONRAD ROENTGEN’s discovery of X-rays in 1895, Becquerel chanced upon the phenomenon that is now known as radioactivity in 1896. The Frenchman believed that Röntgen’s X-rays were responsible for the fluorescence displayed by some substances after being placed in sunlight. Although he was wrong to assume that fluorescence had anything to do with X-rays, he tested large numbers of fluorescent minerals.

He found that uranium, the heaviest element, caused an impression on a covered photographic plate, even after being kept in the dark for several days, and concluded that a phenomenon independent of sunlight induced luminescence.
Investigation isolated the uranium as the source of ‘radioactivity’, a name given to the occurrence by Mme. Curie.

The SI unit of radioactivity, the becquerel is named in his honour.

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  • Radioactivity (aps.org)
  • MARIE CURIE (1867-1934) PIERRE CURIE (1859-1906)

    1898-1902 – France

    ‘Pitchblende, the ore from which uranium is extracted, is much more radioactive than pure uranium. The ore must therefore contain unknown radioactive elements’

    Photograph of marie_curie ©

    MARIE CURIE

    Photograph of pierre_curie ©

    PIERRE CURIE

    Following the discovery of radioactivity by HENRI BECQUEREL (1852-1908) in 1896, Marie Curie conclusively proved that radioactivity is an intrinsic property of the element in question and is not a condition caused by outside factors.

    She correctly concluded that pitchblende contained other, more radioactive elements than uranium.
    The Curies isolated two new radioactive elements, polonium and radium, from pitchblende. The discovery of new elements by their radioactivity was proof that radioactivity was a property of atoms.

    image of two pages from MarieCurie's notebook, which remains radioactive

    Even today, Marie Curie’s notebooks of her studies remain too radioactive to handle.

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    ALBERT EINSTEIN (1879-1955)

    1905 – Switzerland

    1. ‘the relativity principle: All laws of science are the same in all frames of reference.
    2. constancy of the speed of light: The speed of light in a vacuüm is constant and is independent of the speed of the observer’
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    EINSTEIN

    The laws of physics are identical to different spectators, regardless of their position, as long as they are moving at a constant speed in relation to each other. Above all the speed of light is constant. Classical laws of mechanics seem to be obeyed in our normal lives because the speeds involved are insignificant.

    Newton’s recipe for measuring the speed of a body moving through space involved simply timing it as it passed between two fixed points. This is based on the assumptions that time is flowing at the same rate for everyone – that there is such a thing as ‘absolute’ time, and that two observers would always agree on the distance between any two points in space.
    The implications of this principle if the observers are moving at different speeds are bizarre and normal indicators of velocity such as distance and time become warped. Absolute space and time do not exist. The faster an object is moving the slower time moves. Objects appear to become shorter in the direction of travel. Mass increases as the speed of an object increases. Ultimately nothing may move faster than or equal to the speed of light because at that point it would have infinite mass, no length and time would stand still.

    ‘The energy (E) of a body equals its mass (m) times the speed of light (c) squared’

    This equation shows that mass and energy are mutually convertible under certain conditions.

    The mass-energy equation is a consequence of Einstein’s theory of special relativity and declares that only a small amount of atomic mass could unleash huge amounts of energy.

    Two of his early papers described Brownian motion and the ‘photoelectric’ effect (employing PLANCK’s quantum theory and helping to confirm Planck’s ideas in the process).

    1915 – Germany

    ‘Objects do not attract each other by exerting pull, but the presence of matter in space causes space to curve in such a manner that a gravitational field is set up. Gravity is the property of space itself’

    From 1907 to 1915 Einstein developed his special theory into a general theory that included equating accelerating forces and gravitational forces. This implies light rays would be bent by gravitational attraction and electromagnetic radiation wavelengths would be increased under gravity. Moreover, mass and the resultant gravity, warps space and time, which would otherwise be ‘flat’, into curved paths that other masses (e.g. the moons of planets) caught within the field of the distortion follow. The predictions from special and general relativity were gradually proven by experimental evidence.

    Einstein spent much of the rest of his life trying to devise a unified theory of electromagnetic, gravitational and nuclear fields.

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    ROBERT MILLIKAN (1868-1953)

    1909 – USA

    The charge on the electron’

    Photograph of ROBERT ANDREWS MILLIKAN ©

    ROBERT ANDREWS MILLIKAN

    Millikan measured the charge on the electron.

    His experiment showed that the electron is the fundamental unit of electricity; that is, electricity is the flow of electrons.
    From his experiment Millikan calculated the basic charge on an electron to be 1.6 × 10-19 coulomb.
    This charge cannot be subdivided – by convention this charge is called unit negative, -1, charge.

    Millikan also determined that the electron has only about 1/1837 the mass of a proton, or 9.1 × 10-31 kilogram.

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    ERNEST RUTHERFORD (1871-1937)

    1911 Manchester, England

    ‘The atom contains a core or nucleus of very high density and very concentrated positive charge. Most of the atom is empty space, with the electrons moving about the tiny central nucleus’

    Early photograph of ERNEST RUTHERFORD

    ERNEST RUTHERFORD

    Working under JJ THOMSON (1856-1940) at the Cambridge Cavendish Laboratory and later at the McGill University in Montreal, in 1898 Rutherford put forward his observation that radioactive elements give off at least two types of ray with distinct properties, ‘alpha’ and ‘beta’ rays.

    In 1900 he confirmed the existence of ‘gamma’ rays, which remained unaffected by a magnetic force, whilst alpha and beta rays were both deflected in different directions by such an influence. Although both displayed the ability to stab through solid matter, alpha rays were far less penetrating than beta rays.
    He proved through experimental results that they were helium atoms missing two electrons.

    Alpha Beta Particles, Gamma Rays in a Magnetic Field

    Alpha Beta Particles, Gamma Rays in a Magnetic Field

    Alpha rays are in fact positively charged helium atoms that become true helium when they slow down and their charge is neutralised by picking up electrons.
    Beta rays were later shown to be made up of electrons, and gamma rays to have a shorter wavelength than X-rays.

    diagram showing comparative penetrations of Alpha Beta Gamma radiation

    Alpha Beta Gamma radiation

    In Montreal, Rutherford worked with Frederick Soddy and showed that over a period of time, half of the atoms of a radioactive substance could disintegrate. During the process the substance spontaneously transmuted to other elements. During radioactive decay, one kind of atom (radium) was ejecting another kind of atom (helium).

    Working with other elements, Rutherford and Soddy found that each radioactive element had its own characteristic ‘half-life’. After one half-life, a sample retained only half its original radioactivity, after two half-lives a quarter, after three half-lives an eighth. The half-life of thorium emanation, now known as radon, was close to a minute. The half-lives of other radioactive elements ranged from a split-second to many billions of years. That of radium was 1620 years, while uranium had a half-life of 4.5 billion years.

    The concept of half-life provides a way of measuring the age of rocks. As radioactive atoms decay they emit alpha particles. As these are essentially helium atoms, the amount of helium gas accumulates within the pores and fissures of a sample of a uranium mineral as a measure of how many atoms have decayed. Heating samples to drive off their helium and measuring the amount gives an indication of their age.
    In order to provide more reliable dates, measuring the amount of lead, the ultimate decay product, compared with the amount of uranium, eliminates the errors introduced by the escape of some of the helium decay product to the air.

    Dating rocks in this way gives an estimate of the age of the Earth, and by implication also the Sun, of around 4.5 billion years.

    A radioactive atom is simply a heavy atom, which happens to be unstable. Eventually it disintegrates by expelling an alpha, beta or gamma ray. What remains is an atom of a slightly lighter element. A radioactive atom may decay more than once. Uranium, for instance, transforms itself into a succession of lighter and lighter atoms, one of which is radium, until it achieves stability as a non-radioactive atom of lead.

    English: Radioactive decay modes

      

    Working with HANS GEIGER (1882-1945), Rutherford developed the Geiger counter at Manchester University in 1908. This device measured radiation and was used in Rutherford’s work on identifying the make-up of alpha rays.

    While he was at McGill, Rutherford had experimented firing alpha particles at a photographic plate. He had noticed that, while the image produced was sharp; if he passed the alpha particles through thin plates of mica, the resulting image on the photographic plate was diffuse. The particles were clearly being deflected through small angles as they passed close to the atoms of mica.
    In 1910 his team undertook work to examine the results of directing a stream of alpha particles at a piece of platinum foil. While most passed through, about one in eight thousand bounced back – that is, deflected through an angle of more than 90 degrees.

    Deflection of alpha Particles by Thin Metal Foil

    Deflection of alpha Particles by Thin Metal Foil

    In 1911 he put forward the theory that the reason for the rate of deflection was because atoms contained a minute nucleus that bore most of the weight, while the rest of the atom was largely ’empty space’ in which electrons orbited the nucleus much as planets orbit the Sun. The reason that one in eight thousand alpha particles bounced back was because they were striking the positively charged nucleus of an atom, whereas the rest simply passed through the spacious part.

    But what was an atomic nucleus made of?
    At 100,000th the size of the atom, it would take decades of painstaking experiments to discover.

    In 1919, working in collaboration with other scientists, Rutherford artificially induced the disintegration of atoms by collision with alpha particles. In the process the atomic make-up of the element changed as protons were forced out of the nucleus. He transmuted nitrogen into oxygen (and hydrogen) and went on to repeat the process with other elements.

    (image source)

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    WILLIAM HENRY BRAGG (1862-1942) WILLIAM LAWRENCE BRAGG (1890-1971)

    1912 – England

    X-rays scattered from a crystal will show constructive interference provided their wavelength ( λ ) fits the equation

    2d sin θ = n λ 

    where d is the spacing between atoms of the crystal, θ the angle through which the rays have scattered and n is any whole number

    This is the cornerstone of the science of X-ray crystallography.

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    Symmetrically spaced atoms cause re-radiated X...

    Symmetrically spaced atoms cause re-radiated X-rays to reinforce each other in the specific directions where their path-length difference, 2d sin θ, equals an integer multiple of the wavelength λ (Photo credit: Wikipedia)

    NIELS BOHR (1885-1962)

    1913 – Denmark

    ‘Electrons in atoms are restricted to certain orbits but they can move from one orbit to another’

    Bohr’s was the first quantum model for the internal structure of the atom.

    Bohr worked with RUTHERFORD in Manchester and improved upon Rutherford’s model, which said that electrons were free to orbit the nucleus at random.

    Classical physics insisted that electrons moving around the nucleus would eventually expire and collapse into the nucleus as they radiated energy. Bohr resolved the issue surrounding Rutherford’s atomic structure by applying the concept of quantum physics set out by MAX PLANCK in 1900.
    He suggested that the electrons would have to exist in one of a number of specific orbits, each being defined by specific levels of energy. From the perspective of quantum theory, electrons only existed in these fixed orbits where they did not radiate energy. The electrons could move to higher-level orbits if energy was added, or fall to lower ones if they gave out energy. The innermost orbit contains up to two electrons. The next may contain up to eight electrons. If an inner orbit is not full, an electron from an outer orbit can jump into it. Energy is released as light (a photon) when this happens. The energy that is released is a fixed amount, a quantum.

    Quanta of radiation would only ever be emitted as an atom made the transition between states and released energy. Electrons could not exist in between these definite steps. This quantised theory of the electrons’ orbits had the benefits of explaining why atoms always emitted or absorbed specific frequencies of electromagnetic radiation and of providing an understanding of why atoms are stable.

    Bohr calculated the amount of radiation emitted during these transitions using Planck’s constant. It fitted physical observations and made sense of the spectral lines of a hydrogen atom, observed when the electromagnetic radiation (caused by the vibrations of electrons) of the element was passed through a prism.
    The prism breaks it up into spectral lines, which show the intensities and frequencies of the radiation – and therefore the energy emissions and absorptions of the electrons.

    Each of the elements has an atomic number, starting with hydrogen, with an atomic number of one. The atomic number corresponds to the number of protons in the element’s atoms. Bohr had already shown that electrons inhabit fixed orbits around the nucleus of the atom.
    Atoms strive to have a full outer shell (allowed orbit), which gives a stable structure. They may share, give away or receive extra electrons to achieve stability. The way that atoms will form bonds with others, and the ease with which they will do it, is determined by the configuration of electrons.
    As elements are ordered in the periodic table by atomic number, it can be seen that their position in the table can be used to predict how they will react.

    In addition to showing that electrons are restricted to orbits, Bohr’s model also suggested that

    • the orbit closest to the nucleus is lowest in energy, with successively higher energies for more distant orbits.
    • when an electron jumps to a lower orbit it emits a photon.
    • when an electron absorbs energy, it jumps to a higher orbit.

    Bohr called the jump to another orbit a quantum leap.

    Although it contained elements of quantum theory, the Bohr model had its flaws. It ignored the wave character of the electron. Work by WERNER KARL HEISENBERG later tackled these weaknesses.

    Bohr’s theory of complementarity states that electrons may be both a wave and a particle, but that we can only experience them as one or the other at any given time. He showed that contradictory characteristics of an electron could be proved in separate experiments and none of the results can be accepted singly – we need to hold all the possibilities in mind at once. This requires a slight adjustment to the original model of atomic structure, we can no longer say that an electron occupies a particular orbit, but can only give the probability that it is there.

    In 1939 he developed a theory of nuclear fission with Jon Archibald Wheeler (b.1911) and realised that the 235uranium isotope would be more susceptible to fission than the more commonly used 238uranium.
    The element bohrium is named after him.

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    HENRY GWYN JEFFREYS MOSELEY (1887-1915)

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    MXIF

    1914 – Manchester, England

    ‘Moseley’s law – the principle outlining the link between the X-ray frequency of an element and its atomic number’

    ca. 1910s --- Physicist Henry Gwyn Jeffreys MOSELEY --- Library Image by © Bettmann/CORBIS

    MOSELEY

    Working with ERNEST RUTHERFORD’s team in Manchester trying to better understand radiation, particularly of radium, Moseley became interested in X-rays and learning new techniques to measure their frequencies.
    A technique had been devised using crystals to diffract the emitted radiation, which had a wavelength specific to the element being experimented upon.

    In 1913, Moseley recorded the frequencies of the X-ray spectra of over thirty metallic elements and deduced that the frequencies of the radiation emitted were related to the squares of certain incremental whole numbers. These integers were indicative of the atomic number of the element, and its position in the periodic table. This number was the same as the positive charge of the nucleus of the atom (and by implication also the number of electrons with corresponding negative charge).

    By uniting the charge in the nucleus with an atomic number, a vital link had been found between the physical atomic make up of an element and its chemical properties, as indicated by where it sits in the periodic table.
    This meant that the properties of an element could now be considered in terms of atomic number rather than atomic weight, as had previously been the case – certain inconsistencies in the MENDELEEV version of the periodic table could be ironed out. In addition, the atomic numbers and weights of several missing elements could be predicted and other properties deduced from their expected position in the table.

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    LOUIS DE BROGLIE (1892-1987)

    1924 – France

    ‘The wave-particle duality of matter.
    Like photons, particles such as electrons also show wave-particle duality, that is, they also behave like light waves’

    Einstein had suggested in one of his 1905 papers that the ‘photoelectric’ effect could be explained by an interpretation that included electromagnetic waves behaving like particles. De Broglie simply reversed the argument and asked: ‘if waves can behave like particles (a stream of quanta or photons), why should particles not behave like waves?’

    Louis de Broglie (1892-1987), French physicist. De Broglie was instrumental in showing that waves and particles can behave like each other at a quantum level (wave-particle duality). He suggested that particles, such as electrons, could behave as waves. This was confirmed by Davisson and Germer in 1927. He was awarded the 1928 Nobel Prize for Physics for his work.

    LOUIS DE BROGLIE

    By applying quantum theory de Broglie was able to show that an electron could act as if it were a wave with its wavelength calculated by dividing PLANCK‘s constant by the electron’s momentum at any given instant. His proposal was found to be plausible by experimental evidence shortly afterwards.

    BORN, SCHRODINGER and HEISENBERG offered arguments to the debate. NIELS BOHR provided some context in 1927 by pointing out that the equipment used in experiments to prove the case one way or another greatly influenced the outcome of the results. A principle of ‘complementarity’ had to be applied suggesting the experimental proof to be a series of partially correct answers, which have to be interpreted side by side for the most complete picture. Uncertainty and Complementarity together became known as the ‘Copenhagen interpretation’ of quantum mechanics.

    Eventually, the ‘probabilistic’ theories of Heisenberg and Born largely won out. At this juncture, cause and effect had logically been removed from atomic physics and de Broglie, like Einstein and Schrödinger, began to question the direction quantum theory was taking and rejected many of its findings.

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    SATYENDRA NATH BOSE (1894-1974) ALBERT EINSTEIN (1879-1955)

    1924 – India & Germany

    ‘At temperatures close to absolute zero atoms and molecules lose their separate identities and merge into a single ‘super-atom’. This ‘super-atom’ is known as Bose-Einstein condensate’

    Like solid, liquid, gas and plasma (hot ionized gas), Bose-Einstein condensate is a state of matter.

    Photograph of BOSE ©

    BOSE

    Velocity in a gas of rubidium as it is cooled:...

    Velocity in a gas of rubidium as it is cooled: the starting material is on the left, and Bose–Einstein condensate is on the right. (Photo credit: Wikipedia)

    In quantum mechanics, elementary particles can, in some circumstances, behave like waves. The waves – which are waves of probability – describe where a particle is most likely to be at a given moment. The uncertainty principle dictates that it is impossible to know the exact position of a particle. In 1924, while in Germany, Einstein predicted, based on ideas originally suggested by Indian-born Bose, that when atoms approach absolute zero the waves would expand and finally overlap; the elementary particles of which they are composed all merge into a single quantum state.
    This state is now known as Bose-Einstein condensate.

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    WOLFGANG PAULI (1900- 58)

    1925 – Austria

    ‘No two electrons in an atom can have the same quantum number’

    A quantum number describes certain properties of a particle such as its charge and spin.

    An orbital or energy level cannot hold more than two electrons, one spinning clockwise, the other anti-clockwise.

    Electrons are grouped in shells, which contain orbitals. The shells are numbered ( n = 1,2,3 etc. ) outwards from the nucleus. These numbers are the ‘principle quantum numbers’.
    An increase in n indicates an increase in energy associated with the shell, and an increase in the distance of the shell from the nucleus. The number of electrons allowed in a shell is 2n2. Each shell contains sub-shells or energy sub-levels. A shell can only have n sub-shells. A shell is given a number and a letter ( s,p,d,f,g,etc. ). For example, the electron shell structure of lithium is 1s22s1 (two electrons in ‘s’ sub-shell of the first shell, and one electron in ‘s’ sub-shell of the second shell; the superscript indicates the number of electrons in the shell).

    The Pauli principle provided a theoretical basis for the modern periodic table.

    1930 – Austria

    ‘The radioactive beta decay of an atomic nucleus in which a neutron turns into a proton and emits an electron does not seem to follow the law of conservation of energy.’

    To account for the missing energy, Pauli postulated that a particle of zero charge and zero mass is released in such reactions.

    A few years later ENRICO FERMI named the new particle a neutrino.
    There are three known types of neutrino – muon, tau and electron.

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    ERWIN SCHRODINGER (1887-1961)

    1926 Austria

    ‘The complex mathematical equation describing the changing wave pattern of a particle such as an electron in an atom. The solution of the equation gives the probability of finding the particle at a particular place’

    This equation provides a mathematical description of the wave-like properties of particles.

    the Schrodinger equation

    Schrödinger developed what became known as ‘wave mechanics, although like others, including EINSTEIN, he later became uncomfortable with the direction quantum theory took. His own proposal was built upon that of LOUIS DE BROGLIE – that particles could, in quantum theory, behave like waves. Schrödinger felt that de Broglie’s equations were too simplistic and did not offer a detailed enough analysis of the behaviour of matter, particularly at the sub-atomic level. He removed the idea of the particle completely and argued that everything is a form of wave.

    PLANCK’s work had shown that light came in different colours because the photons had different amounts of energy. If you divided that energy by the frequency at which that colour of light was known to oscillate, you always arrived at the same value, the so-called Planck’s constant.

    Between 1925 and 1926 Schrödinger calculated a ‘wave equation’ that mathematically underpinned his argument. When the theory was applied against known values for the hydrogen atom, for example in calculating the level of energy in an electron, it overcame some of the elements of earlier quantum theory developed by NIELS BOHR and addressed the weaknesses of de Broglie’s thesis.
    Schrödinger stated that the quantum energies of electrons did not correspond to fixed orbits, as Bohr had stated, but to the vibration frequency of the ‘electron-wave’ around the nucleus. Just as a piano string has a fixed tone, so an electron wave has a fixed quantum of energy.

    Having done away with particles, it was required that a physical explanation for the properties and nature of matter be found. The Austrian came up with the concept of ‘wave packets’ which would give the impression of the particle as seen in classical physics, but would actually be a wave.

    The probabilistic interpretation of quantum theory based on the ideas of HEISENBERG and BORN proposed that matter did not exist in any particular place at all, being everywhere at the same time until one attempted to measure it. At that point, the equations offered the best ‘probability’ of finding the matter in a given location. Wave mechanics used much simpler mathematics than Heisenberg’s matrix mechanics, and was easier to visualise.
    Schrödinger showed that in mathematical terms, both theories were the same and the rival theories together formed the basis for quantum mechanics.

    Photograph of Schrödinger ©

    ERWIN SCHRODINGER

    Schrödinger joined Einstein and others in condemning the probabilistic view of physics where nothing was explainable for certain and cause and effect did not exist.

    Ironically, PAUL ADRIAN MAURICE DIRAC went on to prove that Schrödinger’s wave thesis and the probabilistic interpretation were, mathematically at least, the equivalent of each other. Schrödinger shared a Nobel Prize for Physics with Dirac in 1933.

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    WERNER HEISENBERG (1901- 76)

    1927 – Germany

    ‘It is impossible to determine exactly both the position and momentum of a particle (such as an electron) simultaneously’

    The principle excludes the existence of a particle that is stationary.

    To measure both the position and momentum ( momentum = mass × velocity ) of a particle simultaneously requires two measurements: the act of performing the first measurement will disturb a particle and so create uncertainty in the second measurement. Thus the more accurately a position is known; the less accurately can the momentum be determined. The disturbance is so small it can be ignored in the macroscopic world, but is quite dramatic for particles in the microscopic world. MAX BORN’S ‘probabilistic’ interpretation, expressed at about the same time, concerning the likelihood of finding a particle at any point through probability defined by the amplitude of its associated wave, led to similar conclusions.
    The uncertainty principle also applies to energy and time. A particle’s kinetic energy cannot be measured with complete precision either.

    Heisenberg suggested the model of the proton and neutron being held together in the nucleus of the atom after the work of JAMES CHADWICK who discovered the neutron in 1932.

    Heisenberg decided to try to develop a new model of the atom, more fundamentally based on quantum theory that worked for all atoms. He believed the approach of trying to visualise a physical model of the atom was destined to fail because of the paradoxical wave-particle nature of electrons.

    Every particle has an associated wave. The position of a particle can be precisely located where the wave’s undulations are most intense. But where the wave’s undulations are most intense, the wavelength is also at its most ill-defined, and the velocity of the associated particle is impossible to determine. Similarly, a particle with a well-defined wavelength has a precise velocity but a very ill-defined position.

    Since the orbits of electrons could not be observed, he decided to ignore them and focus instead on what could be observed and measured, namely, the energy they emitted and absorbed as shown in the spectral lines. He tried to devise a mathematical way of representing the orbits of electrons, and to use this as a way of predicting the atomic features shown up in the spectral lines. He showed that matrix mechanics could account for many of the properties of atoms, including those with more than one electron.

    Together with PAUL DIRAC, Pascual Jordan created a new set of equations based on the rival theories of Schrödinger and Heisenberg, which they called ‘transformation theory’. Whilst studying these equations, Heisenberg noticed the paradox that measurements of position and velocity (speed and direction) of particles taken at the same time gave imprecise results. He believed that this uncertainty was a part of the nature of the sub-atomic world.
    The act of measuring the velocity of a subatomic particle will change it, making the simultaneous measurement of its position invalid.

    An unobserved object is both a particle and a wave. If an experimenter chooses to measure the object’s velocity, the object will transform itself into a wave. If an experimenter chooses to measure its position, it will become a particle. By choosing to observe either one thing or the other, the observer is actually affecting the form the object takes.
    The practical implication of this is that one can never predict where an electron will be at a precise moment, one can only predict the probability of its being there.

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    PAUL DIRAC (1902- 84)

    1928 – UK

    ‘Every fundamental particle has an antiparticle – a mirror twin with the same mass but opposite charge’

    ‘It appears that the simplest Hamiltonian for a point-charge electron satisfying the requirements of both relativity and the general transformation theory leads to an explanation of all duplexity phenomena without further assumption’

    1931 – UK

    ‘A magnetic monopole is analogous to electric charge’

    A magnetic monopole is a hypothetical particle that carries a basic magnetic charge – in effect, a single north or south magnetic pole acting as a free particle.

    Until recently no one has observed a monopole.

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    SIR JAMES CHADWICK (1891-1974)

    1932 Manchester, England

    ‘Discovery of neutrons – elementary particles devoid of any electric charge’

    In contrast with the Helium nuclei (alpha rays) which are charged, and therefore repelled by the electrical forces present in the nuclei of heavy atoms, the neutron is capable of penetrating and splitting the nuclei of even the heaviest elements, creating the possibility of the fission of 235uranium

    Assistant to ERNEST RUTHERFORD, Chadwick’s earlier work involved the showering of elements with alpha particles. The picture that gradually emerged was one of a nucleus that contained a very heavy particle with a positive electric charge. This particle was christened the proton, the hydrogen building block envisaged by WILLIAM PROUT.
    A spin-off of this was the deduction that the nucleus of the hydrogen atom, the positively charged proton with an atomic weight of one was present in larger quantities in the nucleus of every other atom.

    Rutherford and Geiger had shown that a helium atom and an alpha particle were the same thing, apart from the positive electric charge carried by the alpha particle.

    A helium atom seemed to consist of a nucleus of a pair of protons circled by two electrons. However, a helium nucleus seemed to weigh as much as four protons. The mass of the known components of an atom did not add-up. Protons seemed to account for around half of the weight and were matched in number by an equal amount of negatively charged electrons to counter their positive charge. But the weight of an electron was one-thousandth that of a proton, so approximately half of the atomic weight of the element was unaccounted for.
    Chadwick solved the conundrum in 1932 when he re-interpreted the results of an experiment carried out by IRENE and FREDERIC JULIOT-CURIE (Irene was the daughter of PIERRE and MARIE CURIE).
    The couple had found in 1932 that when beryllium was showered with alpha particles, the resultant radiation could force protons out of substances containing hydrogen. Chadwick suggested that neutrally charged sub-atomic units, which he named neutrons, with the same weight as protons, could force this reaction and therefore were what made up the radiation that the Curies called gamma rays. Rutherford had hinted at the existence of such a particle in 1920.

    The explanation was widely accepted and the riddle of `atomic weight’ had been solved: a similar number of neutrons to protons in the nucleus of an element would make up the remaining fifty per cent of the previously ‘missing’ mass.

    photo portrait of FREDERICK SODDY ©

    FREDERICK SODDY (more)

    The discovery of the neutron made sense of the observation that many elements come in a variety of forms, each with differing radioactive properties such as decay rate. Each form consisted of atoms with a different mass. Frederick Soddy christened these variants ‘isotopes’ in 1911. The idea that each element might be a mixture of atoms of different atomic weights explained why the atomic weights of a handful of elements were not simple multiples of the atomic weight of hydrogen, the most notorious example being chlorine whose atomic weight was 35.5 times that of hydrogen. Most of the variant forms of each element turned out to be radioactively unstable. An element such as chlorine, with more than one stable isotope, is rare.

    The various isotopes of an element were merely atoms with the same number of protons in their nucleus but with a different number of neutrons.

    artistic representation of atomic disintegration

    Thus every atom was composed of electrons, protons and neutrons. The protons and neutrons clung together in a central clump – the atomic nucleus – while the electrons circled in a distant haze. The neutrons were responsible for increasing the weight of the elements without adding any electrical charge. Two protons and two neutrons made a helium nucleus; eight protons and eight neutrons an oxygen nucleus; 26 protons and 30 neutrons an iron nucleus; 79 protons and 118 neutrons a gold; and 92 protons and 146 neutrons a nucleus of uranium. When a radioactive nucleus expelled an alpha particle, it lost two neutrons and two protons and consequently became a nucleus of an element two places lower in the periodic table. When a radioactive nucleus emitted a beta particle, however, a neutron changed into a proton, transforming the nucleus into that of an element one place higher in the periodic table.

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    MARCUS OLIPHANT (1901-2000)

    1934 – UK

    ‘Hydrogen has three isotopes: hydrogen-1 (ordinary hydrogen: one proton), hydrogen-2 (deuterium: one proton, one neutron) and hydrogen-3 (tritium: one proton, two neutrons)’

    They each have one single proton (z = 1), but differ in the number of their neutrons. Hydrogen has no neutron, deuterium has one, and tritium has two neutrons. The isotopes of hydrogen have, respectively, mass numbers of one, two, and three. Their nuclear symbols are therefore 1H, 2H, and 3H. The atoms of these isotopes have one electron to balance the charge of the one proton. Since chemistry depends on the interactions of protons with electrons, the chemical properties of the isotopes are nearly the same.

    MARK OLIPHANT

    The lightest rare gas, helium, exists in nature in two forms – two isotopes

    The usual form is represented as 4He, where the figure 4 stands for the number of nucleons in the atomic nucleus (two protons and two neutrons). In the unusual form, 3He, the atomic nucleus has only one neutron, so it is lighter. In helium that occurs naturally the heavier isotope is more frequent than the lighter one by a factor of about 10 million. That is why it is only in the last 50 years that it has been possible to produce large amounts of 3He, at nuclear power stations, for example. At normal temperatures the gases of the two isotopes differ only in their atomic weights.

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    OTTO HAHN (Germany 1879-1968) LEIS MEITNER (Austria 1878-1968) FRITZ STRASSMANN (Germany 1902-1980)

    1938 – Germany

    ‘Nuclear Fission. The breaking up of the nucleus of a heavy atom into two or more lighter atoms. Energy is released during the process’

    A reinterpretation of the results of the mid 1930s neutron-bombarding experiments of ENRICO FERMI with uranium offered an alternative explanation to Fermi’s own idea that the uranium had transmuted into new heavier elements. The three German scientists offered the explanation that the uranium nucleus had in fact been broken down into a number of smaller nuclei

    with the release of potentially huge amounts of energy under the rules of Einstein’s formula E = mc2.

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    LISE MEITNER

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