Definitions

molecule

molecule

[mol-uh-kyool]
molecule [New Lat.,=little mass], smallest particle of a compound that has all the chemical properties of that compound. A single atom is usually not referred to as a molecule, and ionic compounds such as common salt are not made up of molecules. Unlike ions, molecules carry no electrical charge.

Nature of Molecules

Molecules are made up of two or more atoms, either of the same element or of two or more different elements, joined by one or more covalent chemical bonds. According to the kinetic-molecular theory, the molecules of a substance are in constant motion. The state (solid, liquid, or gaseous) in which matter appears depends on the speed and separation of the molecules in the matter. Substances differ according to the structure and composition of their molecules. A molecular compound is represented by its molecular formula; for example, water is represented by the formula H2O. A more complex structural formula is sometimes used to show the arrangement of atoms in the molecule.

Molecules differ in size and molecular weight as well as in structure. In a chemical reaction between molecular substances, the molecules are often broken apart into atoms or radicals that recombine to form other molecules, i.e., other substances. In other cases two or more molecules will combine to form a single larger molecule, or a large molecule will be broken up into several smaller molecules.

Molecules can assume many shapes and sizes. Molecules of hydrogen gas, H2, are very small; each consists of two atoms of hydrogen. Water molecules, H2O, are much larger, containing an atom of oxygen as well as two of hydrogen. The atoms in a water molecule are arranged at the corners of an isosceles triangle; the oxygen atom is located where the two equal sides meet and the angle between these sides is about 105°. A carbon dioxide molecule, CO2, is linear, with the two oxygen atoms an equal distance on either side of the carbon atom. In methane, CH4, the hydrogen atoms are arranged at the corners of a tetrahedron with the carbon atom in the center. In benzene, C6H6, the carbon atoms form a hexagonal ring with a hydrogen atom joined to each carbon atom. More complex molecules resemble rings, chains, helices, or other forms. Many molecules occurring in living organisms are very complex. RNA and DNA molecules resemble giant helices. By polymerization a large number of small molecules may be joined to form a single large polymer molecule. Typical polymers include synthetic resins, rubbers, and plastics.

Evolution of Molecular Theory

The terms atom and molecule were used interchangeably until the early 19th cent. Initial experimental work with gases led to what is essentially the modern distinction. J. A. C. Charles and R. Boyle had shown that all gases exhibit the same relationship between a change in temperature or pressure and the corresponding change in volume. J. L. Gay-Lussac had shown that gases always combine in simple whole-number volume proportions and had rediscovered the earlier findings of Charles, which had not been published.

Dalton's Theory

One early theorist was John Dalton, best known for his atomic theory. Dalton believed that gases were made up of tiny particles, which he thought were atoms. He thought that these atoms were stationary and in contact with one another and that heat was a material substance, called caloric, that was contained in shells around the atom (these shells of caloric were actually what was in contact). When a gas was heated, the amount of caloric was increased, the shells became larger, and the gas expanded. Dalton did not accept Gay-Lussac's findings about combining volumes of gases, perhaps because it could not be explained by his theory.

Avogadro's Hypothesis

A different theory from Dalton's that could explain the combining volumes of gases was proposed by the Italian physicist Amadeo Avogadro in 1811. According to his theory, under given conditions of temperature and pressure, a given volume of any gas contains a definite number of particles. From the earlier observation that one volume of hydrogen gas and one volume of chlorine gas react to form two volumes of hydrogen chloride gas he deduced that the particles in gaseous hydrogen or chlorine could not be single atoms, but must be some combination of atoms. He called this combination a molecule. He reasoned that the two volumes of hydrogen chloride that are formed must contain twice as many particles as either single volume of hydrogen or chlorine. Thus, if there were 100 particles each of hydrogen and chlorine, there would be 200 particles of hydrogen chloride produced; but there could be only 100 particles produced if the original particles of hydrogen and chlorine were indivisible atoms, since each particle of hydrogen chloride contains both hydrogen and chlorine. An assumption that there are two atoms in a molecule of gaseous hydrogen or chlorine and one atom each of hydrogen and chlorine in a molecule of hydrogen chloride preserves both the hypothesis of indivisible atoms and the hypothesis of equal numbers of particles in equal volumes of gases. Similar reasoning would allow a larger even number of atoms in the molecules of hydrogen or chlorine, but Avogadro favored a rule of simplicity, using the smallest possible number. In the model of gases proposed by Avogadro, the particles were not in contact and much of the volume of the gas was empty space.

Cannizaro's Compromise

Avogadro's theory was not well accepted; most responses were very critical. Meanwhile, Dalton's theory prompted extensive experimentation and especially the determination of combining weights of the elements. Many shortcomings of Dalton's theory were uncovered, and although a number of modifications were suggested, none were very successful. It was not until 1858 that the Italian chemist Stanislao Cannizaro suggested a merging of Avogadro's and Dalton's theories. The acceptance of this revised theory was assisted by the acceptance by physicists at about the same time of the kinetic-molecular theory of gases that was first proposed in 1738 by Daniel Bernoulli.

Several methods of representing a molecule's structure. In Lewis structures, element symbols elipsis

Smallest identifiable unit into which a pure substance can be divided and retain its composition and chemical properties. Division into still smaller parts, eventually atoms, involves destroying the bonding that holds the molecule together. For noble gases, the molecule is a single atom; all other substances have two (diatomic) or more (polyatomic) atoms in a molecule. The atoms are the same in elements, such as hydrogen (H2), and different in compounds, such as glucose (C6H12O6). Atoms always combine into molecules in fixed proportions. Molecules of different substances can have the same constituent atoms, either in different proportions, as in carbon monoxide (CO) and carbon dioxide (CO2), or bonded in different ways (see isomer). The covalent bonds in molecules give them their shapes and most of their properties. (The concept of molecules has no significance in solids with ionic bonds.) Analysis with modern techniques and computers can determine and display the size, shape, and configuration of molecules, the positions of their nuclei and electron clouds, the lengths and angles of their bonds, and other details. Electron microscopy can even produce images of individual molecules and atoms. Seealso molecular weight.

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In chemistry, a molecule is defined as a sufficiently stable electrically neutral group of at least two atoms in a definite arrangement held together by very strong chemical bonds. It can also be defined as a unit of two or more atoms held together by covalent bonds. Molecules are distinguished from polyatomic ions in this strict sense. In organic chemistry and biochemistry, the term molecule is used less strictly and also is applied to charged organic molecules and biomolecules.

This definition has evolved as knowledge of the structure of molecules has increased. Earlier definitions were less precise defining molecules as the smallest particles of pure chemical substances that still retain their composition and chemical properties. This definition often breaks down since many substances in ordinary experience, such as rocks, salts, and metals, are composed of large networks of chemically bonded atoms or ions, but are not made of discrete molecules.

In the kinetic theory of gases the term molecule is often used for any gaseous particle regardless of their composition. According to this definition noble gas particles are considered molecules despite the fact that they are composed of a single non-bonded atom.

A molecule may consist of atoms of the same chemical element, as with oxygen (O2), or of different elements, as with water (H2O). Atoms and complexes connected by non-covalent bonds such as hydrogen bonds or ionic bonds are generally not considered single molecules.

No typical molecule can be defined for ionic crystals (salts) and covalent crystals (network solids), although these are often composed of repeating unit cells that extend either in a plane (such as in graphite) or three-dimensionally (such as in diamond or sodium chloride). The theme of repeated unit-cellular-structure also holds for most condensed phases with metallic bonding. In glasses (solids that exist in a vitreous disordered state), atoms may also be held together by chemical bonds without any definable molecule, but also without any of the regularity of repeating units that characterises crystals.

Molecular science

The science of molecules is called molecular chemistry or molecular physics, depending on the focus. Molecular chemistry deals with the laws governing the interaction between molecules that results in the formation and breakage of chemical bonds, while molecular physics deals with the laws governing their structure and properties. In practice, however, this distinction is vague. In molecular sciences, a molecule consists of a stable system (bound state) comprising two or more atoms. Polyatomic ions may sometimes be usefully thought of as electrically charged molecules. The term unstable molecule is used for very reactive species, i.e., short-lived assemblies (resonances) of electrons and nuclei, such as radicals, molecular ions, Rydberg molecules, transition states, van der Waals complexes, or systems of colliding atoms as in Bose-Einstein condensates.

History

The term "molecule", from the French molécule meaning "extremely minute particle," was coined by French philosopher Rene Descartes in the 1620s. Although the existence of molecules was accepted by many chemists since the early 19th century as a result of Dalton's laws of Definite and Multiple Proportions (1803-1808) and Avogadro's law (1811), there was some resistance among positivists and physicists such as Mach, Boltzmann, Maxwell, and Gibbs, who saw molecules merely as convenient mathematical constructs. The work of Perrin on Brownian motion (1911) is considered to be the final proof of the existence of molecules.

Molecular size

Most molecules are far too small to be seen with the naked eye, but there are exceptions. DNA, a macromolecule, can reach macroscopic sizes, as can molecules of many polymers. The smallest molecule is the diatomic hydrogen (H2), with an overall length of roughly twice the 74 picometres (0.74 Å) bond length. Molecules commonly used as building blocks for organic synthesis have a dimension of a few Å to several dozen Å. Single molecules cannot usually be observed by light (as noted above), but small molecules and even the outlines of individual atoms may be traced in some circumstances by use of an atomic force microscope. Some of the largest molecules are macromolecules or supermolecules.

Radius

Effective molecular radius is the size a molecule displays in solution. The table of permselectivity for different substances contains examples.

Molecular formula

A compound's empirical formula is the simplest integer ratio of the chemical elements that constitute it. For example, water is always composed of a 2:1 ratio of hydrogen to oxygen, and ethyl alcohol or ethanol is always composed of carbon, hydrogen, and oxygen in a 2:6:1 ratio. However, this does not determine the kind of molecule uniquely - dimethyl ether has the same ratio as ethanol, for instance. Molecules with the same atoms in different arrangements are called isomers.

The molecular formula reflects the exact number of atoms that compose the molecule and so characterizes different isomers.

The empirical formula is often the same as the molecular formula but not always. For example the molecule acetylene has molecular formula C2H2, but the simplest integer ratio of elements is CH.

The molecular mass can be calculated from the chemical formula and is expressed in conventional atomic mass units equal to 1/12th of the mass of a neutral carbon-12 (12C isotope) atom. For network solids, the term formula unit is used in stoichiometric calculations.

Molecular geometry

Molecules have fixed equilibrium geometries—bond lengths and angles— about which they continuously oscillate through vibrational and rotational motions. A pure substance is composed of molecules with the same average geometrical structure. The chemical formula and the structure of a molecule are the two important factors that determine its properties, particularly its reactivity. Isomers share a chemical formula but normally have very different properties because of their different structures. Stereoisomers, a particular type of isomers, may have very similar physico-chemical properties and at the same time very different biochemical activities.

Molecular spectroscopy

Molecular spectroscopy deals with the response (spectrum) of molecules interacting with probing signals of known energy (or frequency, according to Planck's formula). Molecules are described by quantum mechanics and have quantized energy levels that can be analyzed by detecting the molecule's interaction with electromagnetic radiation through absorbance or emission of energy. Spectroscopy does not generally refer to diffraction studies where particles such as neutrons, electrons, or high energy X-rays interact with a regular arrangement of molecules (as in a crystal).

Theoretical aspects

The study of molecules by molecular physics and theoretical chemistry is largely based on quantum mechanics and is essential for the understanding of the chemical bond. The simplest of molecules is the hydrogen molecule-ion, H2+, and the simplest of all the chemical bonds is the one-electron bond. H2+ is composed of two positively-charged protons and one negatively-charged electron bound by photon exchange, which means that the Schrödinger equation for the system can be solved more easily due to the lack of electron–electron repulsion. With the development of fast digital computers, approximate solutions for more complicated molecules became possible and are one of the main aspects of computational chemistry.

When trying to define rigorously whether an arrangement of atoms is "sufficiently stable" to be considered a molecule, IUPAC suggests that it "must correspond to a depression on the potential energy surface that is deep enough to confine at least one vibrational state". This definition does not depend on the nature of the interaction between the atoms, but only on the strength of the interaction. In fact, it includes weakly-bound species that would not traditionally be considered molecules, such as the helium dimer, He2, which has one vibrational bound state and is so loosely bound that it is only likely to be observed at very low temperatures.

Etymology

According to Merriam-Webster and the Online Etymology Dictionary, the word "molecule" derives from the Latin "moles" or small unit of mass.

  • Molecule (1794) - "extremely minute particle," from Fr. molécule (1678), from Mod.L. molecula, dim. of L. moles "mass, barrier". A vague meaning at first; the vogue for the word (used until late 18th century only in Latin form) can be traced to the philosophy of Descartes.

Most molecules are made up of multiple atoms; for example, a molecule of water is a combination of two hydrogen atoms and one oxygen atom. The term 'molecule' in gases has been used as a synonym for the fundamental particles of the gas, whatever their structure. This definition results in a few types of gases (for example inert elements that do not form compounds, such as neon), which have 'molecules' consisting of only a single atom.

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