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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MAX PLANCK (1856-1947)

1900 – Germany

‘Energy is not a continuous quantity but it is quantised; it flows in discrete packets or quanta. When particles emit energy they do so only in quanta’

According to Quantum theory, the energy (E) of one quantum (photon) is given by E = hf where f is the frequency of radiation and h is Planck’s constant.
Its value is 6.63 x 10-34 joules per second

h is a tiny number, close to zero, but it is has a finite value. This implies energy is released in discrete chunks, a revolutionary notion.

photo portrait of MAX PLANCK ©

MAX PLANCK

By the late 1800s the science of thermodynamics was developing to the point that people were beginning to understand the nature of energy.
The traditional view was that energy was released in a continuous stream and that any amount of energy could be indefinitely divided into smaller and smaller ‘lumps’. Planck’s work on the laws of thermodynamics and black body radiation led him to abandon this classical notion of the dynamic principles of energy and formulate the quantum theory, which assumes that energy changes take place in distinct packages, or quanta, that cannot be subdivided. This successfully accounted for certain phenomena that Newtonian theory could not explain.

The basic laws of thermodynamics recognised that energy could not be created or destroyed, but was always conserved. The second law was drawn from an understanding that heat would not pass from a colder body to a hotter body.
The study of thermodynamics was based on the assumption that matter was ultimately composed of particles. LUDWIG BOLTZMAN had proposed an explanation of thermodynamics, saying the energy contained in a system is the collective result of the movements of many tiny particles rattling around. He believed the second law was only valid in a statistical sense; it only worked if you added up all the bits of energy in all the little particles.
Among his detractors was Max Karl Ernst Ludwig Planck.

Planck began his work on the second law of thermodynamics and the concept of entropy. He investigated how materials transform between solid, liquid and gaseous states. In doing so he found explanations for the laws governing the differing freezing and boiling points of various substances.
He also looked at the conduction of electricity through liquid solutions (electrolysis).

In the mid 1890s Planck turned his attention to the question of how heated substances radiate energy. Physicists were aware that all bodies radiate heat at all frequencies – although maximum radiation is emitted only at a certain frequency, which depends on the temperature of the body. The hotter the body, the higher the frequency for maximum radiation. (Frequency is the rate per second of a wave of any form of radiation).

Planck had been considering formulae for the radiation released by a body at high temperature. Using ideas developed by ROBERT KIRCHOFF, he knew it should be expressible as a combination of wavelength frequency and temperature. For a theoretical ‘black body’, physicists could not predict expressions that were in line with the behaviour of hot bodies at high frequencies and were in agreement with other equations showing their nature at low frequencies. Thus no law could be found which fitted all frequencies and obeyed the laws of classical physics simultaneously.
Plank resolved to find a theoretical formula that would work mathematically, even if it did not reflect known physical laws. His first attempts were partially successful, but did not take into account any notion of particles or quanta of energy, as he was certain of the continuous nature of energy. In an ‘act of despair’ he renounced classical physics and embraced quanta.

The final straw had been a concept developed by John Rayleigh and James Jeans that became known as the ‘ultraviolet catastrophe’ theory. They had developed a formula that predicted values for radiation distribution and worked at low frequencies, but not at high frequencies. It was at odds with Planck’s formula, which worked for high frequencies but broke down at low frequencies. In June 1900 Rayleigh had pointed out that classical mechanics, when applied to the oscillators of a black-body, leads to an energy distribution that increases in proportion to the square of the frequency. This conflicted with all known data.

Planck’s answer was to introduce what he called ‘energy elements’ or quanta and to express the energy emitted as a straightforward multiplication of frequency by a constant, which became known as ‘Planck’s constant’ (6.6256 x 10-34 Jsec-1). This only works with whole number multiples which means for the formula to have any practical use one must accept the radical theory that energy is only released in distinct, non-divisible chunks, known as ‘quanta’, or for a single chunk of energy, a ‘quantum’. This completely contradicts classical physics, which assumed that energy is emitted in a continuous stream. The individual quanta of energy were so small that when emitted at the everyday large levels observed, it appears that energy could seem to be flowing in a continuous stream.
Thus classical physics was cast into doubt and quantum theory was born.

Planck announced his theory on December 14 1900 in his paper ‘On the Theory of the Law of Energy Distribution in the Continuous Spectrum’. Planck said ‘energy is made up of a completely determinate number of finite equal parts, and for this purpose I use the constant of nature h = 6.55 x 10-27(erg sec)’

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When ALBERT EINSTEIN was able to explain the ‘photoelectric’ effect in 1905, suggesting that light is emitted in quanta called ‘photons’, by applying Planck’s theory – and likewise NIELS BOHR in his explanation of atomic theory in 1913 – the abstract idea was shown to explain physical phenomena.

Planck was awarded the Nobel Prize for Physics in 1918.

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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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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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