The division of a sample of a substance into progressively smaller parts produces no change in either its composition or its chemical properties until parts consisting of single molecules are reached. Further subdivision of the substance leads to still smaller parts that usually differ from the original substance in composition and always differ from it in chemical properties. In this latter stage of fragmentation the chemical bonds that hold the atoms together in the molecule are broken.
Atoms consist of a single nucleus with a positive charge surrounded by a cloud of negatively charged electrons. When atoms approach one another closely, the electron clouds interact with each other and with the nuclei. If this interaction is such that the total energy of the system is lowered, then the atoms bond together to form a molecule. Thus, from a structural point of view, a molecule consists of an aggregation of atoms held together by valence forces. Diatomic molecules contain two atoms that are chemically bonded. If the two atoms are identical, as in, for example, the oxygen molecule (O2), they compose a homonuclear diatomic molecule, while if the atoms are different, as in the carbon monoxide molecule (CO), they make up a heteronuclear diatomic molecule. Molecules containing more than two atoms are termed polyatomic molecules, e.g., carbon dioxide (CO2) and water (H2O). Polymer molecules may contain many thousands of component atoms.
Not all substances are made up of distinct molecular units. Sodium chloride (common table salt), for example, consists of sodium ions and chlorine ions arranged in a lattice so that each sodium ion is surrounded by six equidistant chlorine ions and each chlorine ion is surrounded by six equidistant sodium ions. The forces acting between any sodium and any adjacent chlorine ion are equal. Hence, no distinct aggregate identifiable as a molecule of sodium chloride exists. Consequently, in sodium chloride and in all solids of similar type, the concept of the chemical molecule has no significance. Therefore, the formula for such a compound is given as the simplest ratio of the atoms, called a formula unit—in the case of sodium chloride, NaCl.
Molecules are held together by shared electron pairs, or covalent bonds. Such bonds are directional, meaning that the atoms adopt specific positions relative to one another so as to maximize the bond strengths. As a result, each molecule has a definite, fairly rigid structure, or spatial distribution of its atoms. Structural chemistry is concerned with valence, which determines how atoms combine in definite ratios and how this is related to the bond directions and bond lengths. The properties of molecules correlate with their structures; for example, the water molecule is bent structurally and therefore has a dipole moment, whereas the carbon dioxide molecule is linear and has no dipole moment. The elucidation of the manner in which atoms are reorganized in the course of chemical reactions is important. In some molecules the structure may not be rigid; for example, in ethane (H3CCH3) there is virtually free rotation about the carbon-carbon single bond.
The nuclear positions in a molecule are determined either from microwave vibration-rotation spectra or by neutron diffraction. The electron cloud surrounding the nuclei in a molecule can be studied by X-ray diffraction experiments. Further information can be obtained by electron spin resonance or nuclear magnetic resonance techniques. Advances in electron microscopy have enabled visual images of individual molecules and atoms to be produced. Theoretically the molecular structure is determined by solving the quantum mechanical equation for the motion of the electrons in the fieldof the nuclei (called the Schrödinger equation). In a molecular structure the bond lengths and bond angles are those for which the molecular energy is the least. The determination of structures by numerical solution of the Schrödinger equation has become a highly developed process entailing use of computers and supercomputers.
Atom, smallest unit into which matter can be divided without the release of electrically charged particles. It also is the smallest unit of matter that has the characteristic properties of a chemical element. As such, the atom is the basic building block of chemistry.
Most of the atom is empty space. The rest consists of a positively charged nucleus of protons and neutrons surrounded by a cloud of negatively charged electrons. The nucleus is small and dense compared with the electrons, which are the lightest charged particles in nature. Electrons are attracted to any positive charge by their electric force; in an atom, electric forces bind the electrons to the nucleus.
Because of the nature of quantum mechanics, no single image has been entirely satisfactory at visualizing the atom’s various characteristics, which thus forces physicists to use complementary pictures of the atom to explain different properties. In some respects, the electrons in an atom behave like particles orbiting the nucleus. In others, the electrons behave like waves frozen in position around the nucleus. Such wave patterns, called orbitals, describe the distribution of individual electrons. The behaviour of an atom is strongly influenced by these orbital properties, and its chemical properties are determined by orbital groupings known as shells.
Most matter consists of an agglomeration of molecules, which can be separated relatively easily. Molecules, in turn, are composed of atoms joined by chemical bonds that are more difficult to break. Each individual atom consists of smaller particles—namely, electrons and nuclei. These particles are electrically charged, and the electric forces on the charge are responsible for holding the atom together. Attempts to separate these smaller constituent particles require ever-increasing amounts of energy and result in the creation of new subatomic particles, many of which are charged.
All atoms are roughly the same size, whether they have 3 or 90 electrons. Approximately 50 million atoms of solid matter lined up in a row would measure 1 cm (0.4 inch). A convenient unit of length for measuring atomic sizes is the angstrom (Å), defined as 10−10 metre. The radius of an atom measures 1–2 Å. Compared with the overall size of the atom, the nucleus is even more minute. It is in the same proportion to the atom as a marble is to a football field. In volume the nucleus takes up only 10−14metres of the space in the atom—i.e., 1 part in 100,000. A convenient unit of length for measuring nuclear sizes is the femtometre (fm), which equals 10−15 metre. The diameter of a nucleus depends on the number of particles it contains and ranges from about 4 fm for a light nucleus such as carbon to 15 fm for a heavy nucleus such as lead. In spite of the small size of the nucleus, virtually all the mass of the atom is concentrated there. The protons are massive, positively charged particles, whereas the neutrons have no charge and are slightly more massive than the protons. The fact that nuclei can have anywhere from 1 to nearly 300 protons and neutrons accounts for their wide variation in mass. The lightest nucleus, that of hydrogen, is 1,836 times more massive than an electron, while heavy nuclei are nearly 500,000 times more massive.