3.

Early History of Atomic Theories

The history of atomic theories is full of success and failure stories for hundreds of chemists. In textbooks such as this one, only the success of a few is documented. However, the success of these chemists was often facilitated by both the success and failure of many others. Recall that by the use of deductive logic the Greeks (for example, Democritus) in about 300 B.C. hypothesized that matter cut into smaller and smaller pieces would eventually reach what they called the atom literally meaning indivisible. This idea was reintroduced over two thousand years later by an English chemist/schoolteacher named John Dalton in 1805. He re-created the modern theory of atoms to explain three important scientific laws the laws of definite composition, multiple proportions, and conservation of mass. The success of Daltons theory of the atom was that it could explain all three of these laws and much more. Daltons theory was that the smallest piece of matter was an atom that was indivisible, and that an atom was different from one element to another. All atoms of a particular element were thought to be exactly the same. Daltons model of the atom was that of a featureless sphere by analogy, a billiard ball (Figure 1). Daltons atomic theory lasted for about a century, although it came under increasing criticism during the latter part of the 1800s.

Figure 1 In Daltons atomic model, an atom is a solid sphere, similar to a billiard ball. This simple model is still used today to represent the arrangement of atoms in molecules.

DID YOU

KNOW

William Crookes (18321919) William Crookes was the eldest of sixteen children and inherited his fathers fortune, made in real estate. This enabled him to lead a leisurely life, and also to conduct scientific research in many areas of chemistry and physics. Crookes is best known for his cathode ray tube, which was made possible by his improvements to the vacuum pump and Voltas invention of the electric cell. His vacuum techniques later made mass production of the light bulb practical.

SUMMARY
Table 1

Creating the Dalton Atomic Theory (1805)

Theoretical explanation Each atom has a particular combining capacity. Some atoms have more than one combining capacity. Atoms are neither created nor destroyed constant in a chemical reaction. Atomic theory Matter is composed of indestructible, indivisible atoms, which are identical for one element, but different from other elements.

Key experimental work Law of definite composition: elements combine in a characteristic mass ratio Law of multiple proportions: there may be more than one mass ratio Law of conservation of mass: total mass remains

The Thomson Atomic Model

The experimental studies of Svante Arrhenius and Michael Faraday with electricity and chemical solutions and of William Crookes with electricity and vacuum tubes suggested that electric charges were components of matter. J. J. Thomsons quantitative experiments with cathode rays resulted in the discovery of the electron, whose charge was later measured by Robert Millikan. The Thomson model of the atom (1897) was a hypothesis that the atom was composed of electrons (negative particles) embedded in a positively charged sphere (Figure 2(a)). Thomsons research group at Cambridge University in England used mathematics to predict the uniform three-dimensional distribution of

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the electrons throughout the atom. The Thomson model of the atom is often communicated by using the analogy of a raisin bun, with the raisins depicting the electrons and the bun being the positive material of his atom (Figure 2(b)).

INVESTIGATION 3.1.1
The Nature of Cathode Rays (p. 209) The discovery of cathode rays led to a revision of the Dalton atomic model. What are their properties?

(a)

(b)

Figure 2 (a) In Thomsons atomic model, the atom is a positive sphere with embedded electrons. (b) This model can be compared to a raisin bun, in which the raisins represent the negative electrons and the bun represents the region of positive charge.

SUMMARY
Table 2

Creating the Thomson Atomic Theory (1897)

Theoretical explanation Atoms may gain or lose electrons to form ions in solution. Particular atoms and ions gain or lose a specific number of electrons. Electricity is composed of negatively charged particles. Electrons are a component of all matter. Electrons have a specific fixed electric charge. Atomic theory Matter is composed of atoms that contain electrons (negative particles) embedded in a positive material. The kind of element is characterized by the number of electrons in the atom.

DID YOU

KNOW

Key experimental work Arrhenius: the electrical nature of chemical solutions Faraday: quantitative work with electricity and solutions Crookes: qualitative studies of cathode rays Thomson: quantitative studies of cathode rays Millikan: charged oil drop experiment

Rutherford Quotes You know it is about as incredible as if you fired a 350-mm shell at a piece of tissue paper and it came back and hit you. Now I know what the atom looks like. 1911 The electrons occupy most of the space in the atom, like a few flies in a cathedral. The notion that nuclear energy could be controlled is moonshine. 1933

The Rutherford Atomic Theory

One of Thomsons students, Ernest Rutherford (Figure 3), eventually showed that some parts of the Thomson atomic theory were not correct. Rutherford developed an expertise with nuclear radiation during the nine years he spent at McGill University in Montreal. He worked with and classified nuclear radiation as alpha ( ), beta ( ), and gamma ( ) helium nuclei, electrons, and high-energy electromagnetic radiation from the nucleus, respectively. Working with his team of graduate students he devised an experiment to test the Thomson model of the atom. They used radium as a source of alpha radiation, which was directed at a thin film of gold. The prediction, based on the Thomson model, was that the alpha particles should be deflected little, if at all. When some of the alpha particles were deflected at large angles and even backwards from the foil, the prediction
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Figure 3 Rutherfords work with radioactive materials at McGill helped prepare him for his challenge to Thomsons atomic theory. Atomic Theories 163

ACTIVITY 3.1.1
Rutherfords Gold Foil Experiment (p. 210) Rutherfords famous experiment involved shooting atomic bullets at an extremely thin sheet of gold. You can simulate his experiment.

Prediction alpha particles metal foil Evidence alpha particles metal foil

was shown to be false, and the Thomson model judged unacceptable (Figure 4). Rutherfords nuclear model of the atom was then created to explain the evidence gathered in this scattering experiment. Rutherfords analysis showed that all of the positive charge in the atom had to be in a very small volume compared to the size of the atom. Only then could he explain the results of the experiment (Figure 5). He also had to hypothesize the existence of a nuclear (attractive) force, to explain how so much positive charge could occupy such a small volume. The nuclear force of attraction had to be much stronger than the electrostatic force repelling the positive charges in the nucleus. Even though these theoretical ideas seemed far-fetched, they explained the experimental evidence. Rutherfords explanation of the evidence gradually gained widespread acceptance in the scientific community.

SUMMARY
Table 3

Creating the Rutherford Atomic Theory (1911)

Theoretical explanation The positive charge in the atom must be concentrated in a very small volume of the atom. A very strong nuclear force holds the positive charges within the nucleus. Most of the atom is empty space. Atomic theory An atom is composed of a very tiny nucleus, which contains positive charges and most of the mass of the atom. Very small negative electrons occupy most of the volume of the atom.

Key experimental work Rutherford: A few positive alpha particles are deflected at large angles when fired at a gold foil. Most materials are very stable and do not fly apart (break down). Rutherford: Most alpha particles pass straight through gold foil.

Figure 4 Rutherfords experimental observations were dramatically different from what he had expected based on the Thomson model.

Protons, Isotopes, and Neutrons

nucleus

atom

Figure 5 To explain his results, Rutherford suggested that an atom consisted mostly of empy space, explaining why most of the alpha particles passed nearly straight through the gold foil.

1 proton ( 0p or p+) a positively charged subatomic particle found in the nucleus of atoms

The Thomson model of the atom (1897) included electrons as particles, but did not describe the positive charge as particles; recall the raisins (electrons) in a bun (positive charge) analogy. The Rutherford model of the atom (1911) included electrons orbiting a positively charged nucleus. There may have been a hypothesis about the nucleus being composed of positively charged particles, but it was not until 1914 that evidence was gathered to support such a hypothesis. Rutherford, Thomson, and associates studied positive rays in a cathode ray tube and found that the smallest positive charge possible was from ionized hydrogen gas. Rutherford reasoned that this was the fundamental particle of positive charge and he named it the proton, meaning first. (Again Rutherford showed his genius by being able to direct the empirical work and then interpret the evidence theoretically.) By bending the hydrogen-gas positive rays in a magnetic field they were able to determine the charge and mass of the hypothetical proton. The proton was shown to have a charge equal to but opposite to that of the electron and a mass 1836 times that of an electron. All of this work was done in gas discharge tubes that evolved into the version of the mass spectrometer (Figure 6) developed by Francis Aston during the period 19191925. Evidence from radioactivity and mass spectrometer investigations falsified Daltons theory that all atoms of a particular element were identical. The evidence indicated that

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magnet slit gas discharge tube

sample inlet

slit detector

magnet

beam of positive ions

Figure 6 A mass spectrometer is used to determine the masses of ionized particles by measuring the deflection of these particles as they pass through the field of a strong magnet.

there were, for example, atoms of sodium with different masses. These atoms of different mass were named isotopes, although their existence could not yet be explained. Later, James Chadwick, working with Rutherford, was bombarding elements with alpha particles to calculate the masses of nuclei. When the masses of the nuclei were compared to the sum of the masses of the protons for the elements, they did not agree. An initial hypothesis was that about half of the mass of the nucleus was made up of protonelectron (neutral) pairs. However, in 1932 Chadwick completed some careful experimental work involving radiation effects caused by alpha particle bombardment. He reasoned that the only logical and consistent theory that could explain these results involved the existence of a neutral particle in the nucleus. According to Chadwick, the nucleus would contain positively charged protons and neutral particles, called neutrons. The different radioactive and mass properties of isotopes could now be explained by the different nuclear stability and different masses of the atom caused by different numbers of neutrons in the nuclei of atoms of a particular element.

isotope ( A X) a variety of atoms of Z an element; atoms of this variety have the same number of protons as all atoms of the element, but a different number of neutrons

1 neutron ( 0n or n) a neutral (uncharged) subatomic particle present in the nucleus of atoms

SUMMARY

Rutherford Model

An atom is made up of an equal number of negatively charged electrons and postively charged protons. Most of the mass of the atom and all of its positive charge is contained in a tiny core region called the nucleus. The nucleus contains protons and neutrons that have approximately the same mass. The number of protons is called the atomic number (Z). The total number of protons and neutrons is called the mass number (A).

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SUMMARY
Table 4

Creating the Concepts of Protons, Isotopes, and Neutrons

Theoretical explanation The smallest particle of positive charge is the proton. Isotopes of an element have a fixed number of protons but varying stability and mass. The nucleus contains neutral particles called neutrons. Atomic theory Atoms are composed of protons, neutrons, and electrons. Atoms of the same element have the same number of protons and electrons, but may have a varying number of neutrons (isotopes of the element).

Key experimental work Rutherford (1914): The lowest charge on an ionized gas particle is from the hydrogen ion Soddy (1913): Radioactive decay suggests different atoms of the same element Aston (1919): Mass spectrometer work indicates different masses for some atoms of the same element Radiation is produced by bombarding elements with alpha particles.

Section 3.1 Questions

Understanding Concepts
1. Summarize, using labelled diagrams, the evolution of

Making Connections
9. State some recent examples of stories in the news media

atomic theory from the Dalton to the Rutherford model.

2. Present the experimental evidence that led to the

that mention or refer to atoms.

10. Describe some contributions Canadian scientists and/or

Rutherford model.
3. How did Rutherford infer that the nucleus was

scientists working in Canadian laboratories made to the advancement of knowledge about the nature of matter.

(a) very small (compared to the size of the atom)? (b) positively charged?
4. (a) State the experimental evidence that was used in the

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Extension

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discovery of the proton. (b) Write a description of a proton.

5. (a) State the experimental evidence that was used in the

11. Rutherfords idea that atoms are mostly empty space is

discovery of the neutron. (b) Describe the nature of the neutron. Applying Inquiry Skills
6. What is meant by a black box and why is this an appro-

retained in all subsequent atomic theories. How can solids then be solid? In other words, how can your chair support you? Why doesnt your pencil go right through the atoms that make up your desk?
12. When you look around you, the matter you observe can be

priate analogy for the study of atomic structure?

7. Theories are often created by scientists to explain scientific

laws and experimental results. To some people it seems strange to say that theories come after laws. Compare the scientific and common uses of the term theory.
8. What is the ultimate authority in scientific work (what kind

of knowledge is most trusted)?

said to be made from electrons, protons, and neutrons. Modern scientific theories tell us something a little different about the composition of matter. For example, today protons are not considered to be fundamental particles; i.e., they are now believed to be composed of still smaller particles. According to current nuclear theory, what is the composition of a proton? Which Canadian scientist received a share of the Nobel Prize for his empirical work in verifying this hypothesis of sub-subatomic particles?

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