The Uniqueness of Water I. Introduction A. About 70% of the globe is covered by water.

Life as we know it thrives on this planet because we have water here and because of water's unique properties. Everything about the physical and chemical properties of ware are unusual. Also, many of the geological processes operating near the surface require or are affected by the presence or absence of water. No other planet in our solar system has been shown to have substantial amounts of liquid water on its surface. B. Water is such an effective absorber of, and transport agent for, heat and such an effective solvent because of the nature of the bonding between water molecules and in the minerals and compounds that are found as solids on the Earth's surface. II. Brief Review of Chemical Bonding A. As we discussed previously matter is made of atoms and atoms are composed of a dense, positively charged nucleus which is surrounded by a cloud of negatively charged, very light weight electrons. These electrons are arranged in layers located at different distances from the nucleus. B. Scientists have discovered that the most stable arrangement of electrons is one in which the outer layer or shell contains the maximum possible number of electrons. For the innermost shell this is 2 electrons, but for all the surrounding outer shells this is 8 electrons. Only the INERT GASSES have filled outer shells as neutral atoms. C. Neutral atoms with unfilled outer shells tend to gain or lose electrons and to combine with other elements in order to achieve the stable outer shell configuration. 1. As an example - hydrogen has only one proton and therefore only one electron. Therefore it has a strong tendency to combine with other elements in such a way as to lose its electron. 2.Oxygen, which is the eighth element in the periodic has 8 protons in its nucleus 8 electrons around it. 2 electrons in its inner shell and 6 in its outer shell. Therefore, it has a strong tendency to pick up 2 electrons to fill its outer shell. D. There are two main ways in which atoms achieve filled outer shells of electrons. They combine with other atoms to form two major types of bonds ionic and covalent. 1. When atoms that have similar tendencies in terms of

whether they want to give up or accept electrons form a compound they form a covalent bond by sharing. If the electrons are equally shared they spend approximately equal amounts of around the two atomic nuclei. a. Oxygen has 8 electrons and therefore needs 2 more for a filled outer shell. Hydrogen on the other hand has a single electron in its 1 shell and is therefore a likely candidate to combine with oxygen in the ratio of two hydrogens to one oxygen to provide a full compliment of outer electrons for all three members of the molecule. E. In the case of the water molecule these electrons are not shared equally between the two elements because H and O have very differentelectronegativities. That is, the shared electrons do not spend completely equal amounts of time orbiting around each atom in the bond. III. Molecular structure of water A. In the case of the water molecule oxygen tends to control the shared electron for a larger proportion of the time than does the hydrogen atom, because it has a much higher electronegativity. The result is that the region around the oxygen atom is generally negatively charged and the region around the hydrogen atoms are positively charged. Furthermore, as you can see from this diagram, both of the hydrogen atoms are located on the same side of the water molecule giving this side of the water molecule a distinctly positively-charged character. B. The water molecule is therefore called a dipolar molecule because of this separation of charges around it. The dipolar nature of the water molecule and the resultant hydrogen bonds that form between water molecules are largely responsible for its uniqueness. 1. These hydrogen bonds are 10-50 X weaker than the covalent bonds that hold the H and O together within the water molecule, but they are still strong enough to cause water molecules to stick together (Picture in center of hand-out). C. If the water molecules existed as totally individual entities, water's properties would be similar to other compounds of low molecular weight. IV. Structure of liquid water A. Introduction 1. Not completely solved yet 2. Behavior described by two different models: continuum

and mixture B. The Continuum Model envisions that the majority of H-bonds are distorted or bent but not broken to form a continuous, irregular network of water molecules. C. The Mixture models envision water as consisting of a mixture of several different types of water molecules. The Cluster model portrayed on Figure 3.3 of the hand-out is an example. Here isolated molecules surround ice-like clusters of H-bonded molecules. V. Unique properties of water (summarized in Table 1.1) A. Thermal properties 1. Melting and boiling points - Water melts and boils at an amazingly high temperature for a compound made up of such light elements. Figure 1.4 shows the melting and boiling points of water compared to those of some similar compounds that form between hydrogen and the other elements of group VI-A in the periodic table. (hydrogen sulfide, hydrogen selenide and hydrogen telluride.) Notice how the temperatures of water are way out of line with that which would be predicted by the behavior of the other similar compounds. a. The reason for the high melting and boiling temperatures is the hydrogen bonding between water molecules that causes them to stick together and to resist being pulled apart which is what happens when ice melts and water boils to become a gas. These bonds are so strong because of the very large electronegativity difference between H and O. Pair H-O H-S H - Se H - Te D electronegativity 1.4 0.4 0.3 0

b. Importance

2. Heat Capacity - The heat capacity of a compound is a measure of how difficult it is to get the molecules of the compound to vibrate. Because after all temperature is just a measure of molecular motion - the more the

molecules of a compound vibrate - the higher the temperature of the compound. Because of the hydrogen bonding of water molecules it is very difficult to get them to vibrate compared to the molecules of any other common substance. Water is therefore said to have a high heat capacity. a. Importance = Since water can absorb a lot of heat with only a small increase in temperature, the temperatures of large standing bodies of water remain relatively constant. This thermal buffering protects life on Earth from possibly lethal D T. b. Water has the highest heat capacity of any known liquid (1 cal / g / deg) except ammonia. 3. Latent heats of fusion and vaporization - measures how much heat you must add to a substance to melt or vaporize it once you have increased the temperature to its melting and boiling points. The excessive energy needed to melt and boil H2O is due to the H-bonds. a. Importance = Liquid water can absorb a lot of heat at one place on the Earth (such as in the Tropics) when evaporation occurs and then transport this heat somewhere else where the water cools, condenses and releases the stored heat. This means that evaporation dissipates much of the Sun's energy thus moderating and stabilizing Earth's surface temperature without appreciable change in the ocean temperature. This heat storage and transportation also has significant consequences for climates and storms such as hurricanes. In fact, evaporations dissipates about 23% of the sun's energy. b. One of the highest of all liquids Latent heat of fusion (80 cal/cm3) Latent heat of vaporization (540 cal/cm3) c. Study the "Change-of-state" diagram on the handout and be able to calculate the amount of heat energy necessary to convert a given number of cm3 of ice at some starting temperature to a vapor.

B. Density TRANSPARENCY 1. Because of the unique bonding & structure of the water molecule ice is less dense at the freezing point than liquid water. From 0 - 4 o the density of the liquid increases with increasing temperature and above 4 o the density decreases with increasing temperature like other liquids. Therefore, when water freezes the ice floats on top of the denser liquid water instead of sinking to the bottom. This is different from most compounds which are denser in the solid state than in the liquid state (Hand-out figure 1.3). a. Ice has low density because of its open structure which results from complete H-bonding which holds the molecules apart. When ice melts, H-bonds break and molecules pack more closely together. b. Importance - Freshwater lakes in mid-latitudes don't freeze solid. Instead ice floats on top and like a blanket, insulates the rest of the lake from freezing temperatures. c. Because of its dissolved salts seawater does not show this anomalous density behavior. C. Solvent Properties - dipolar liquids like water are excellent solvents for ionically-bonded substances such as NaCl. Water is probably the best solvent in nature. That is, it is good at dissolving solids into ions in solution. The dipolar water molecules attach their charged ends to the oppositely charged atoms of solid substances immersed in them and pull components of the solid into the solution as dissolved ions. Ionic substances are most susceptible to this because they have isolated regions of positive and negative charge. 1. In addition to tearing the molecules and atoms of salts apart water keeps them as separate ions in solution by the VI. Role of water in crustal processes A. Introduction 1. Solvent (discussed above) 2. Carrier 3. Catalyst (speeds up chemical reactions)

B. Water as a medium for transporting ions in the geochemical cycle. 1. When an ion is released from a crystal lattice it is immediately surrounded by water molecules because the charge on its surface attracts the water dipole. 2. Subsequent behavior of ion is determined by whether the water molecules are attracted more strongly to other water molecules or to the ion (i.e., whether the ion will be hydrated and stay in solution or precipitate out. 3. The strength of the ion-water molecule attractive force for ions of like charge varies according to the inverse square of the ionic radius.