2.2: The Discovery of Atomic Structure

Learning Objectives

• To become familiar with the components and structure of the atom.

Long before the end of the 19th century, it was well known that applying a high voltage to a gas contained at low pressure in a sealed tube (called a gas discharge tube) caused electricity to flow through the gas, which then emitted light (Figure $$\PageIndex{1}$$). Researchers trying to understand this phenomenon found that an unusual form of energy was also emitted from the cathode, or negatively charged electrode; this form of energy was called a cathode ray.

In 1897, the British physicist J. J. Thomson (1856–1940) proved that atoms were not the most basic form of matter. He demonstrated that cathode rays could be deflected, or bent, by magnetic or electric fields, which indicated that cathode rays consist of charged particles (Figure $$\PageIndex{2}$$). More important, by measuring the extent of the deflection of the cathode rays in magnetic or electric fields of various strengths, Thomson was able to calculate the mass-to-charge ratio of the particles. These particles were emitted by the negatively charged cathode and repelled by the negative terminal of an electric field. Because like charges repel each other and opposite charges attract, Thomson concluded that the particles had a net negative charge; these particles are now called electrons. Most relevant to the field of chemistry, Thomson found that the mass-to-charge ratio of cathode rays is independent of the nature of the metal electrodes or the gas, which suggested that electrons were fundamental components of all atoms.

Subsequently, the American scientist Robert Millikan (1868–1953) carried out a series of experiments using electrically charged oil droplets, which allowed him to calculate the charge on a single electron. With this information and Thomson’s mass-to-charge ratio, Millikan determined the mass of an electron:

$\dfrac {mass}{charge} \times {charge} ={mass}$

It was at this point that two separate lines of investigation began to converge, both aimed at determining how and why matter emits energy. The video below shows how JJ Thompson used such a tube to measure the ratio of charge over mass of an electron

Measuring e/m For an Electron. Video from Davidson College demonstrating Thompson's e/m experiment.

The second line of investigation began in 1896, when the French physicist Henri Becquerel (1852–1908) discovered that certain minerals, such as uranium salts, emitted a new form of energy. Becquerel’s work was greatly extended by Marie Curie (1867–1934) and her husband, Pierre (1854–1906); all three shared the Nobel Prize in Physics in 1903. Marie Curie coined the term radioactivity (from the Latin radius, meaning “ray”) to describe the emission of energy rays by matter. She found that one particular uranium ore, pitchblende, was substantially more radioactive than most, which suggested that it contained one or more highly radioactive impurities. Starting with several tons of pitchblende, the Curies isolated two new radioactive elements after months of work: polonium, which was named for Marie’s native Poland, and radium, which was named for its intense radioactivity. Pierre Curie carried a vial of radium in his coat pocket to demonstrate its greenish glow, a habit that caused him to become ill from radiation poisoning well before he was run over by a horse-drawn wagon and killed instantly in 1906. Marie Curie, in turn, died of what was almost certainly radiation poisoning.

Building on the Curies’ work, the British physicist Ernest Rutherford (1871–1937) performed decisive experiments that led to the modern view of the structure of the atom. While working in Thomson’s laboratory shortly after Thomson discovered the electron, Rutherford showed that compounds of uranium and other elements emitted at least two distinct types of radiation. One was readily absorbed by matter and seemed to consist of particles that had a positive charge and were massive compared to electrons. Because it was the first kind of radiation to be discovered, Rutherford called these substances α particles. Rutherford also showed that the particles in the second type of radiation, β particles, had the same charge and mass-to-charge ratio as Thomson’s electrons; they are now known to be high-speed electrons. A third type of radiation, γ rays, was discovered somewhat later and found to be similar to the lower-energy form of radiation called x-rays, now used to produce images of bones and teeth.

These three kinds of radiation—α particles, β particles, and γ rays—are readily distinguished by the way they are deflected by an electric field and by the degree to which they penetrate matter. As Figure $$\PageIndex{3}$$ illustrates, α particles and β particles are deflected in opposite directions; α particles are deflected to a much lesser extent because of their higher mass-to-charge ratio. In contrast, γ rays have no charge, so they are not deflected by electric or magnetic fields. Figure $$\PageIndex{5}$$ shows that α particles have the least penetrating power and are stopped by a sheet of paper, whereas β particles can pass through thin sheets of metal but are absorbed by lead foil or even thick glass. In contrast, γ-rays can readily penetrate matter; thick blocks of lead or concrete are needed to stop them.

The Atomic Model

Once scientists concluded that all matter contains negatively charged electrons, it became clear that atoms, which are electrically neutral, must also contain positive charges to balance the negative ones. Thomson proposed that the electrons were embedded in a uniform sphere that contained both the positive charge and most of the mass of the atom, much like raisins in plum pudding or chocolate chips in a cookie (Figure $$\PageIndex{6}$$).

In a single famous experiment, however, Rutherford showed unambiguously that Thomson’s model of the atom was incorrect. Rutherford aimed a stream of α particles at a very thin gold foil target (Figure $$\PageIndex{7a}$$) and examined how the α particles were scattered by the foil. Gold was chosen because it could be easily hammered into extremely thin sheets, minimizing the number of atoms in the target. If Thomson’s model of the atom were correct, the positively-charged α particles should crash through the uniformly distributed mass of the gold target like cannonballs through the side of a wooden house. They might be moving a little slower when they emerged, but they should pass essentially straight through the target (Figure $$\PageIndex{7b}$$). To Rutherford’s amazement, a small fraction of the α particles were deflected at large angles, and some were reflected directly back at the source (Figure $$\PageIndex{7c}$$). According to Rutherford, “It was almost as incredible as if you fired a 15-inch shell at a piece of tissue paper and it came back and hit you.”

Rutherford’s results were not consistent with a model in which the mass and positive charge are distributed uniformly throughout the volume of an atom. Instead, they strongly suggested that both the mass and positive charge are concentrated in a tiny fraction of the volume of an atom, which Rutherford called the nucleus. It made sense that a small fraction of the α particles collided with the dense, positively charged nuclei in either a glancing fashion, resulting in large deflections, or almost head-on, causing them to be reflected straight back at the source.

Although Rutherford could not explain why repulsions between the positive charges in nuclei that contained more than one positive charge did not cause the nucleus to disintegrate, he reasoned that repulsions between negatively charged electrons would cause the electrons to be uniformly distributed throughout the atom’s volume.Today it is known that strong nuclear forces, which are much stronger than electrostatic interactions, hold the protons and the neutrons together in the nucleus. For this and other insights, Rutherford was awarded the Nobel Prize in Chemistry in 1908. Unfortunately, Rutherford would have preferred to receive the Nobel Prize in Physics because he considered physics superior to chemistry. In his opinion, “All science is either physics or stamp collecting.”

The historical development of the different models of the atom’s structure is summarized in Figure $$\PageIndex{8}$$. Rutherford established that the nucleus of the hydrogen atom was a positively charged particle, for which he coined the name proton in 1920. He also suggested that the nuclei of elements other than hydrogen must contain electrically neutral particles with approximately the same mass as the proton. The neutron, however, was not discovered until 1932, when James Chadwick (1891–1974, a student of Rutherford; Nobel Prize in Physics, 1935) discovered it. As a result of Rutherford’s work, it became clear that an α particle contains two protons and neutrons, and is therefore the nucleus of a helium atom.

Rutherford’s model of the atom is essentially the same as the modern model, except that it is now known that electrons are not uniformly distributed throughout an atom’s volume. Instead, they are distributed according to a set of principles described by Quantum Mechanics. Figure $$\PageIndex{9}$$ shows how the model of the atom has evolved over time from the indivisible unit of Dalton to the modern view taught today.

Summary

Atoms are the ultimate building blocks of all matter. The modern atomic theory establishes the concepts of atoms and how they compose matter. Atoms, the smallest particles of an element that exhibit the properties of that element, consist of negatively charged electrons around a central nucleus composed of more massive positively charged protons and electrically neutral neutrons. Radioactivity is the emission of energetic particles and rays (radiation) by some substances. Three important kinds of radiation are α particles (helium nuclei), β particles (electrons traveling at high speed), and γ rays (similar to x-rays but higher in energy).