Water Properties James D. Oster Department of Favironmental Sciences, University of California Riverside, Riverside, California, USA. INTRODUCTION Water's physical and chemical properties are uniquely different from other substances in ways that determine, to a large extent, the nature of the physics and biology of the earth. Individual water molecules can link with each other through hydrogen bonds. The degree of hydrogen bonding between water molecules changes with temperature that causes changes in the density of water and its heat content. These changes are uniquely important to the sustainability of life on earth. The dis sociation of water into hydrogen and hydroxyl ions, although very small, is important in reactions of acids and bases. These topics, which were chosen as the focus of this article, are only the “tip-of-the-iceberg™ as is evident when one peruses the references cited here. Waters large heat capacity (752s(eol K)-") plays a key role in providing an environment that makes life possibl. as we know it. The Gult Stream, which ows from the Gulf of Mexico to the Arctic Ocean, cools about 20°C releasing, in the process, energy at a rate equivalent o that released by burning 175 million met- Fic tons of coal pet hous. All the coal mined anally would supply energy’ at this rate for only 12he. Thus the beat released from the cooling of warm ocean cur rents is responsible for the temperate climate over ‘much of the earth's surface!" The physical properties of water ure used to define the following physical constants and units: 1) the freez ing point of water is taken as 0°C and the boiling point at atmospheric pressure is taken as 100°C; 2) the unit of volume in the metric systems is chosen so that ImL of water at 3.98°C weighs 1.000 g; 3) the unit of heat, the calorie, is the amount of heat required to raise the temperature of I g of water by I°C at 15°C. MOLECULAR STRUCTURE The water molecule, H,O, consists of two atoms of hydrogen (H) and one atom of oxygen (0). The orien- tations of the electron orbitals in the oxygen atom and the location of the hydrogen atoms result in a water molecule that can be visualized as a pyramid (Fig. 1), Simplistically, the water molecule can be thought of 14 as an O atom with two hydrogen atoms attached near its surface on one side causing this side of the molecule to have a small positive charge that is matched with a small negative charge on the other side. This resulting separation of the positive and negative charges on the water molecule is called an electric dipole: water has a large electric dipole moment. HYDROGEN BONDING AND ITS ROLE IN THE ‘STRUCTURE OF ICE, WATER, AND STEAM Each hydrogen in one water molecule can bond with the negatively charged oxygen side of another in what is known as a hydrogen bond, Each water molecule can form four hydrogen bonds that extend in four directions. This resulting structure, known as a tetra- hedron, is illustrated in Fig. 2. This arrangement exists among all water molecules in ice: the tetrahedrons form a lattice with others that can be represented as sheets of hexagonal rings (Fig. 3). This structure is a very open, more open than what exists in water. As a result, ice is less dense than water. [An interesting consequence of this difference in density ‘occurs as lakes cool during the winter. lee forms on the surface of lakes rather than on the lake bottom. This provides insulation slowing the rate of freezing and ‘makes it les likely that all the water in lakes will freeze during the winter. Another consequence is that when water freezes in plants, the aevompanying expansion can cause cell walls to break, killing the cell. For ‘example, oranges when ripe can be ruined for the Fresh fruit market by prolonged temperatures below Freez ing. As the juice within an orange freezes, the edible portion of the orange becomes mushy because the cell walls are broken. When this occurs oranges must be harvested quickly for the juice market When ice melts, the hexagonal rings are partially degraded because some of the hydrogen bonds are bro- ken. Consequently, water molecules are packed more closely together, causing water to have a greater density than ice, With an increase in temperature from 0 to 4C, further ring degradation and breaking of hydrogen bonds occur, causing a further increase in the density of water. Only at temperatures greater‘Water Propetis Fig. 1 Geomet shape of the water molecule than 4°C does water begin to show the usual decrease in density with increasing temperature: normal expansion occurs because molecular agitation increases the distance between water molecules and overcomes the effect of hexagonal ring degradation. Water vapor at 100°C, or steam, consists of mostly single water molecules. Because high temperatures increase the ability of molecules to move, the chances fare small that two or more molecules in steam remain together due to H-bonding. WATER AS A SOLVENT FOR SALTS. ‘The reasons that water is so effective in dissolving salts ‘are due to its dipolar character and its shape. Because of the former it hydrates the ions of salts. Because of a combination of ionic character and shape, the attrac- tive force between solvated ions are reduced making them less likely to precipitate out of solution. Due to its dipolar character, water molecules tend to combine with ions to form hydrated ions. This hydration process releases enough energy to overcome the lattice energy holding the ions together in a salt PRD Fig, 2 The tetrahederal arrangement between four water molecules resulting from hydrogen bonds, shown as broken lines, between individual molecules, rs Q o) rearoen (9) Oo-G o6 © i Gog Fig. 3. The lattice of hexagonal ings of water molecules that exists among all water molecules in ice. crystal. Salt crystals consist of negative and positive ions. For example, table salt consists of negatively charged chloride ions and positively charged sodium ions. Each negative ion attracts the positive ends of water molecules, and holds several water molecules to itself. Positive ions, which are usually smaller than negative ions, show this effect more strongly; each positive ion attracts the negative ends of the water molecules and binds several molecules to itself. Gener- ally speaking, the greater the ratio of an ion’s charge to its surface area, the more heavily hydrated it will be Hydration is least significant tor singly charg such as chloride and nitrate, which are considerably larger than most cations. The dissolution of salts by water is also related to it dielectric constant, another aspect of its shape and electric characteristic. When water molecules are sub. jected to electrostatically charged plates, they align their positive ends toward the negative plate and their negative ends toward the positive plate. This par tially neutralizes the applied file stant of water at room temperature is about 80. This compares to a dielectric constant for air of one. The force of attraction, or repulsion, of electric charges is inversely proportional to the dielectric constant of the medium surrounding the charges. This means that two oppositely charged ions in water attract each other with a force of 1/80 as strong as in air. Salts are not as soluble in solvents with low dielectric constants, such as gasoline or acetone as they are in water Thus not only does water tend to hydrate both the positive and negative ions in a salt crystal releasing enough energy to overcome the lattice energy, the force of attraction between the solvated ions is low because of water's high dielectric constant. the dielectric con1326 DISSOCIATION OF WATER In addition to its role as a solvent, water also plays a snificant role in reactions of chemical species known as acids and bases. This stems from the dissociation of water into hydrogen (H~) and hydroxyl (OH™) ions according to the reaction H,0 2H OH ‘The equilibrium expression for this reaction is Ky — [Hx (OHT — 10 x 10 where Ky is known as the dissociation constant of water, and the ions within brackets represent their molar concentrations. According to the dissociation constant of water, only a few HO molecules dissociate. In 1L of pure water, there are about 55 moles of HO and 0.000001 (1x 107) mol each of H™ and OH™. The product of these ion concentrations equals 1.0 x 107" as it should according to the equation for the dissociation constant of water. A solution where the concentration of both (H-] and [OH] equals 1 10~? mol L~! is known as a neutral solution, A water solution where [H™] exceeds [OH7]is said to be acidic. On the other hand, where [OHA] exceeds [H™], the water solution is said to be basic. Using such small numbers to characterize acidity anid basicity 1s difficult, In 1909 Sorensen proposed an alternative method by introducing a term known as pH, where logio(H The pH of a neutral solution is —logig{l x 10-7] which equals 7. For acidic solutions the hydrogen ion concentrations will be greater than 1x 10-7 and their pH = ~ logio 1H] Water Properties ‘Table 1 pH of some common liquids Lemon juice Human blood Tomato juice 30 Human saliva 65-75 Beer 45° Wine 28-38 Cow's milk 6.366 Drinking water 6.5.8.0 Cons mi 666 Drinking water 6580 Source From RAPT Table 193 pH will be less than 7. For basic solutions the hydro. gen ion concentrations will be less than 1 > 107 and their pH will be greater than 7 (Table 1). CONCLUSION ‘The combination of one oxygen atom with two atoms of hydrogen results in a molecule with a small negative charge on one side and a small positive charge on the other. This distribution of charges results in bonding between water molecules. This bonding, known as, H-bonding, causes water to have unique changes in density upon freezing and a high heat capacity. Both fare important to the sustainability of life on earth, ‘The small negative and positive charges on the water molecule play a key role in its ability to dissolve salts. Although the bonds between the oxygen and hydrogen atoms in water are strong, in a liter of water, a very small fraction of the water molecules dissociate into OH™ and H™ ions. This dissociation is the key to the definition of pH and t the understanding of acid ‘and base reactions. REFERENCES L. Franks, F. Water, The Royal Society of Chemistry London, 1984, 2. Masterson, W.Ls 4th Ed; W. B.S lowinski, EJ. Chemical Principles, jundets Co.: Philadelphia, 1977.