water
Introduction
Sections in this article:
Ice
In ice, each molecule forms the maximum number of hydrogen bonds, resulting in crystals composed of open, hexagonal columns. Because these crystals have a number of open regions and pockets, normal ice is less dense than water. However, other forms of ice also exist at conditions of higher pressure, each of these different forms (designated ice II, ice III, etc.) having greater density and other distinct physical properties that differ from those of normal ice, or ice I. As many as eight different forms of ice have been distinguished in this manner. The higher pressures creating such forms cause rearrangements of the hexagonal columns in ice, although the basic kinked hexagonal ring is common to all forms.
When ice melts, it is thought that the fragments of these structures fill many of the gaps that existed in the crystal lattice, making water denser than ice. This tendency is the dominant one between 0℃ and 4℃, at which temperature water reaches its maximum density. Above this temperature, expansion due to the increased thermal energy of the molecules is the dominant factor, with a consequent decrease in density.
Liquid Water
According to present theories, water in the liquid form contains three different molecule populations. At the highest temperatures single molecules are the rule, with little hydrogen bonding because of the high thermal energy of the molecules. In the middle range of temperatures there is more hydrogen bonding, and clusters of molecules are formed. At lower temperatures aggregates of clusters also form, these aggregates being the most common arrangement below about 15℃. On the basis of these three population types and the transitions between them, many aspects of the anomalous behavior of water can be explained. For example, the tendency of water to freeze faster if it has been cooled rapidly from a relatively warm temperature than if it has been cooled at the same rate from a lower temperature is explained in terms of the greater number of irregularly shaped cluster aggregates in the cooler water that must find a suitable means of fitting together with a neighboring aggregate.
The discovery in the late 1960s of “superwater,” or “polywater,” helped to shed light on some aspects of the structure of water. This substance was thought by some to be a giant polymer of water molecules, 40 times denser and 15 times more viscous than ordinary water. Studies showed, however, that these new and unexplained properties were connected with the presence of contaminants in the water. Even so, the interaction of the water molecules with these other substances may be helpful in understanding the way in which water molecules interact with each other.
Structure of the Water Molecule
Many of the physical and chemical properties of water are due to its structure. The atoms in the water molecule are arranged with the two H–O bonds at an angle of about 105° rather than on directly opposite sides of the oxygen atom. The asymmetrical shape of the molecule arises from a tendency of the four electron pairs in the valence shell of oxygen to arrange themselves symmetrically at the vertices of a tetrahedron around the oxygen nucleus. The two pairs associated with covalent bonds (see chemical bond) holding the hydrogen atoms are drawn together slightly, resulting in the angle of 105° between these bonds. This arrangement results in a polar molecule, since there is a net negative charge toward the oxygen end (the apex) of the V-shaped molecule and a net positive charge at the hydrogen end. The electric dipole gives rise to attractions between neighboring opposite ends of water molecules, with each oxygen being able to attract two nearby hydrogen atoms of two other water molecules. Such hydrogen bonding, as it is called, has also been observed in other hydrogen compounds. Although considerably weaker than the covalent bonds holding the water molecule together, hydrogen bonding is strong enough to keep water liquid at ordinary temperatures; its low molecular weight would normally tend to make it a gas at such temperatures.
Various other properties of water, such as its high specific heat, are due to these hydrogen bonds. As the temperature of water is lowered, clusters of molecules form through hydrogen bonding, with each molecule being linked to others by up to four hydrogen bonds, each oxygen atom tending to surround itself with four hydrogen atoms in a tetrahedral arrangement. Hexagonal rings of oxygen atoms are formed in this way, with alternate atoms in either a higher or lower plane than their neighbors to create a kinked three-dimensional structure.
Chemical and Physical Properties
Chemically, water is a compound of hydrogen and oxygen, having the formula H2O. It is chemically active, reacting with certain metals and metal oxides to form bases, and with certain oxides of nonmetals to form acids. It reacts with certain organic compounds to form a variety of products, e.g., alcohols from alkenes. Because water is a polar compound, it is a good solvent. Although completely pure water is a poor conductor of electricity, it is a much better conductor than most other pure liquids because of its self-ionization, i.e., the ability of two water molecules to react to form a hydroxide ion, OH−, and a hydronium ion, H3O+. Its polarity and ionization are both due to the high dielectric constant of water.
Water has interesting thermal properties. When heated from 0℃, its melting point, to 4℃, it contracts and becomes more dense; most other substances expand and become less dense when heated. Conversely, when water is cooled in this temperature range, it expands. It expands greatly as it freezes; as a consequence, ice is less dense than water and floats on it. Because of hydrogen bonding between water molecules, the latent heats of fusion and of evaporation and the heat capacity of water are all unusually high. For these reasons, water serves both as a heat-transfer medium (e.g., ice for cooling and steam for heating) and as a temperature regulator (the water in lakes and oceans helps regulate the climate).
Bibliography
See D. Eisenberg and W. Kauzmann,
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