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SOLUTIONS AND COLLOIDS

We more frequently encounter systems having more than one component. Such systemsfor example, air, smoke, sea water, milk, blood, and rocksare mixtures. If a mixture is uniform throughout at the molecular level, we call it a homogeneous mixture or, more commonly, a solution. Air and sea water, for example, are both solutions. They are clear and transparent. In contrast, in most rocks, we can see distinct regions separated from each other by well-defined boundaries. Such rocks are heterogeneous mixtures. Another example is a mixture of sand and sugar. We can easily distinguish between the two components; the mixing does not occur at the molecular level. Thus mixtures are classified on the basis of how they look to the unaided eye. Some systems, however, fall between homogeneous and heterogeneous mixtures. Cigarette smoke, milk, and blood plasma may look homogeneous, but they do not have the transparency of air or sea water. These mixtures are classified as colloidal dispersions (suspensions).

Although mixtures can contain many components, we will generally restrict our discussion here to two-component systems, with the understanding that everything we say can be extended to multicomponent systems.
Systems containing more than one component are mixtures. o Homogeneous mixtures are uniform throughout. o Heterogeneous mixtures exhibit well-defined boundaries between phases. o When a solution consists of a solid or gas dissolved in a liquid, the liquid acts as the solvent, and the solid or gas is the solute. o When one liquid is dissolved in another, the liquid present in greater amount is considered to be the solvent. The solubility of a substance is the maximum amount of the substance that dissolves in a given amount of solvent at a given temperature.

o o

"Like dissolves like" means that polar molecules are soluble in polar solvents and that nonpolar molecules are soluble in nonpolar solvents. The solubility of solids and liquids in liquids usually increases with increasing temperature; the solubility of gases in liquids usually decreases with increasing temperature.

Percent concentration is given in either weight per unit volume of solution (w/v), weight per unit weight of solvent (w/w), or volume of solute per unit volume of solution (v/v). o Molarity is the number of moles of solute in 1 L of solution. Water is the most important solvent because it dissolves polar compounds and ions through hydrogen bonding and dipole-dipole interactions. o Hydrated ions are surrounded by water molecules (solvation layer) that move together with the ion, cushioning it from collisions with other ions. o Aqueous solutions of ions and molten salts are electrolytes and conduct electricity. Colloids exhibit a scattering of light called the Tyndall effect). o They also exhibit a chaotic random motion, called Brownian motion. o Colloids are stable mixtures despite the relatively large size of the colloidal particles (1 to 1000 nm). o The stability results from the solvation layer that cushions the colloids from direct collisions and from the electric charge on the surface of colloidal particles. Colligative properties are properties that depend only on the number of solute particles present. o Freezing-point depression and osmotic pressure are two examples of colligative properties. o Osmotic pressure operates across an osmotic semipermeable membrane that allows only solvent molecules to pass but screens out all other molecules. In osmotic pressure calculations, concentration is measured in osmolarity, which is the molarity of the solution multiplied by the number of particles produced by dissociation of the solute. Red blood cells in hypotonic solution swell and burst, a process called hemolysis. o Red blood cells in hypertonic solution shrink, a process called crenation. o Some semipermeable membranes allow small solute molecules to pass through along with solvent molecules. In dialysis, such membranes are used to separate large molecules from smaller ones

REACTION RATES AND CHEMICAL EQUILIBRIA Some chemical reactions take place rapidly; others are very slow. For example, glucose and oxygen gas react with each other to form water and carbon dioxide:

This reaction is extremely slow, however. A box of glucose exposed to in the air shows no measurable change even after many years. In contrast, consider what happens when you take one or two aspirin tablets for a slight headache. Very often, the pain disappears in half an hour or so. Thus the aspirin must have reacted with compounds in the body within that time.

Many reactions occur even faster. For example, if we add a solution of silver nitrate (AgNO3) to a solution of sodium chloride (NaCl), a precipitate of silver chloride (AgCl) forms almost instantaneously. The net ionic equation is as follows:

This reaction is essentially complete in considerably less than 1 s. The study of reaction rates is called chemical kinetics. The rate of a reaction is the change in concentration of a reactant (or product) per unit time. Every reaction has its own rate, which must be measured in the laboratory. Consider the following reaction carried out in the solvent acetone:

To determine the reaction rate, we can measure the concentration of the product, iodomethane (CH3I), in the acetone at periodic time intervalssay, every 10 min. For example, the concentration might increase from 0 to 0.12 mol/L over a period of 30 min. The rate of the reaction is the change in the concentration of iodomethane divided by the time interval:

This unit is read "0.0040 mole per liter per minute." During each minute of the reaction, an average of 0.0040 mol of chloromethane, (CH3CI), is converted to iodomethane for each liter of solution. The rate of a reaction is not constant over a long period of time. At the beginning, in most reactions, the change in concentration is directly proportional to time. This period is shown as the linear portion of the curve in Figure 7.1. The rate calculated during this period, called the initial rate, is constant during this time interval. Later, as the reactant is used up, the rate of reaction decreases.

The rates of chemical reactionsboth the ones that we carry out in the laboratory and the ones that take place inside our bodiesare very important. A reaction that goes more slowly than we need may be useless, whereas a reaction that goes too fast may be dangerous. Ideally, we would like to know what causes the enormous variety in reaction rates. In the next three sections, we examine this question.

Some reactions are fast; others are slow. o The rate of a reaction is the change in concentration of a reactant or a product per unit time. o Reactions take place when molecules or ions collide. o The rate of a reaction increases with an increasing number of effective collisionsthat is, collisions that lead to a reaction. o The energy necessary for a reaction to begin is the activation energy. o Effective collisions are those that have (1) more than the activation energy required for the reaction to proceed forward and (2) the proper orientation in space. The lower the activation energy, the faster the reaction. o An energy diagram shows the progress of a reaction. o The position at the top of the curve is called the transition state. Reaction rates generally increase with increasing concentration and temperature; they also depend on the nature of the reactants. o The rate of some reactions can be increased by adding a catalyst, which provides a pathway with a lower activation energy. The rate constant that gives the relationship between the rate of the reaction and the concentration of the reactants remains constant at a constant temperature. Many reactions are reversible and eventually reach equilibriumsome slowly, others quickly. o At equilibrium, the forward and reverse reactions take place at equal rates, and concentrations do not change.

o Every equilibrium has an equilibrium expression and an equilibrium constant, K, which does not change when concentrations change but does change when temperature changes. o The equilibrium constant is large for some reactions and small for others. K and the rate of a reaction are not related. Le Chatelier's principle tells us what happens when we put stress on a system in equilibrium. o The addition of a component causes the equilibrium to shift to the opposite side. o The removal of a component causes the equilibrium to shift to the side from which the component is taken. o Increasing the temperature drives an exothermic equilibrium to the side of the reactants. o Addition of a catalyst has no effect on the position of equilibrium.

ACIDS AND BASES We frequently encounter acids and bases in our daily lives. Oranges, lemons, and vinegar are examples of acidic foods, and sulfuric acid is in our automobile batteries. As for bases, we take antacid tablets for heartburn and use household ammonia as a cleaning agent. What do these substances have in common? Why are acids and bases usually discussed together? In 1884, a young Swedish chemist named Svante Arrhenius (1859-1927) answered the first question by proposing what was then a new definition of acids and bases. According to the Arrhenius definition, an acid is a substance that produces H3O+ ions in aqueous solution, and a base is a substance that produces OH- ions in aqueous solution. This definition of acid is a slight modification of the original Arrhenius definition, which was that an acid produces hydrogen ions, H+. Today we know that ions cannot exist in water. A H+ ion is a bare proton, and a charge of +1 is too concentrated to exist on such a tiny particle (Section 3.2). Therefore, a H+ ion in water immediately combines with an H2O molecule to give a hydronium ion, H3O+.

Apart from this modification, the Arrhenius definitions of acid and base are still valid and useful today, as long as we are talking about aqueous solutions. When an acid dissolves in water, it reacts with the water to produce H3O+. For example, hydrogen chloride, HCl, in its pure state is a poisonous, choking gas. When HCl dissolves in water, it reacts with a water molecule to give hydronium ion and chloride ion:

Thus a bottle labeled aqueous "HCl" is actually not HCl at all, but rather an aqueous solution of and ions in water. We can show the transfer of a proton from an acid to a base by using a symbol called a curved arrow. First we write the Lewis structure of each reactant and product. Then we use curved arrows to show the change in position of electron pairs during the reaction. The tail of the curved arrow is located at the electron pair. The head of the curved arrow shows the new position of the electron pair.

In this equation, the curved arrow on the left shows that an unshared pair of electrons on oxygen forms a new covalent bond with hydrogen. The curved arrow on the right shows that the pair of electrons of the H - C1 bond is given entirely to chlorine to form a chloride ion. Thus, in the reaction of HCl with H2O, a proton is transferred from HCl to H2O and, in the process, an bond forms and an bond is broken. With bases, the situation is slightly different. Many bases are metal hydroxides, such as KOH, NaOH, Mg(OH)2 and Ca(OH)2. These compounds are ionic solids and, when they dissolve in water, their ions merely separate, and each ion is solvated by water molecules (Section 6.6). For example,

Other bases are not hydroxides. Instead, they produce ions in water by reacting with water molecules. The most important example of this kind of base is ammonia, a poisonous, choking gas. When ammonia dissolves in water, it reacts with water to produce ammonium ions and hydroxide ions.

Ammonia is a weak base and the position of the equilibrium for its reaction with water lies considerably toward the left. In a 1.0 M solution of NH3 in water, for example, only about 4 molecules of NH3 out of every 1000 react with water to form NH4+ and OH-. Thus, when ammonia is dissolved in water, it exists primarily as NH3 molecules. Nevertheless, some OH- ions are produced and, therefore, NH3 is a base. Bottles of NH3 in water are sometimes labeled "ammonium hydroxide" or "NH4OH " but this gives a false impression of what is really in the bottle. Most of the NH3 molecules have not reacted with the water, so the bottle contains mostly NH3 and H2O and only a little NH4+ and OH-. We indicate how the reaction of ammonia with water takes place by using curved arrows to show the transfer of a proton from a water molecule to an ammonia molecule. Here, the curved arrow on the left shows that the unshared pair of electrons on nitrogen forms a new covalent bond with a hydrogen of a water molecule. At the same time as the new N H bond forms, an O H bond of a water molecule breaks and the pair of electrons forming the H O bond moves entirely to oxygen forming OH-.

Thus ammonia produces an ion by taking from a water molecule and leaving behind. By the Arrhenius definitions, acids are substances that produce H3O+ ions in aqueous solution, and bases are substances that produce OH- ions in aqueous solution. o A strong acid reacts completely or almost completely with water to form H3O+ ions.

o A strong base reacts completely or almost completely with water to form OH- ions. The Bronsted-Lowry definitions expand the definitions of acid and base to beyond water: An acid is a proton donor, and a base is a proton acceptor. o Every acid has a conjugate base, and every base has a conjugate acid. o The stronger the acid, the weaker its conjugate base. o Conversely, the stronger the base, the weaker its conjugate acid. o An amphiprotic substance, such as water, can act as either an acid or a base. o In an acid-base reaction, the position of equilibrium favors the reaction of the stronger acid and the stronger base to form the weaker acid and the weaker base. The strength of a weak acid is expressed by its ionization constant, Ka. o The larger the value of Ka, the stronger the acid pKa = - log [Ka]. o Acids react with metals, metal hydroxides, and metal oxides to give salts, which are ionic compounds made up of cations from the base and anions from the acid. o Acids also react with carbonates, bicarbonates, ammonia, and amines to give salts. In pure water, a small percentage of molecules undergo self-ionization:

As a result, pure water has a concentration of 10-7 M for H3O+ and 10-7 M for OH-. o The ion product of water, Kw, is equal to 1.0 X 10-14. pKw = 14. Hydronium ion concentrations are generally expressed in pH units, with pH = log [H3O+]. pOH = - log [OH-]. o Solutions with pH less than 7 are acidic; those with pH greater than 7 are basic. o A neutral solution has a pH of 7. o The pH of an aqueous solution is measured with an acid-base indicator or with a pH meter. o Aqueous solutions of salts of strong acids and weak bases are acidic; those of weak acids and strong bases are basic; and those of strong acids and strong bases are neutral. We can measure the concentration of aqueous solutions of acids and bases by using a titration.

o In an acid-base titration, a base of known concentration is added to an acid of unknown concentration (or vice versa) until an end point is reached, at which point the acid or base being titrated is completely neutralized. A buffer does not change its pH very much when either hydronium ions or hydroxide ions are added to it. o Buffer solutions consist of approximately equal concentrations of a weak acid and its conjugate base. o The buffer capacity depends on both its pH and its concentration. The most effective buffer solutions have a pH equal to the pKa of the weak acid. The greater the concentration of the weak acid and its conjugate base, the greater the buffer capacity. The most important buffers for blood are carbonate and phosphate. The Henderson-Hasselbalch equation is a mathematical relationship between pH, the pKa of a weak acid, and the concentrations of the weak acid and its conjugate base:

ORGANIC CHEMISTRY (REVIEW) Organic chemistry is the chemistry of the compounds of carbon. As you study Chapters 10-18 (organic chemistry) and 19-31 (biochemistry), you will see that organic compounds are everywhere around us. They are in our foods, flavors, and fragrances; in our medicines, toiletries, and cosmetics; in our plastics, films, fibers, and resins; in our paints, varnishes, and glues; and, of course, in our bodies and the bodies of all other living organisms. Perhaps the most remarkable feature of organic compounds is that they involve the chemistry of carbon and only a few other elementschiefly, hydrogen, oxygen, and nitrogen. While the majority of organic compounds contain carbon and just these three elements, many also contain sulfur, a halogen (fluorine, chlorine, bromine, or iodine), or phosphorus. Organic chemistry concentrates on carbon. The chemistry of the other elements comes under the field of inorganic chemistry. Carbon is far from being among the most abundant elements in Earth's crust. In

terms of elemental abundance, approximately 75% of Earth's crust is composed of just two elements: oxygen and silicon. These two elements are the components of silicate minerals, clays, and sand. In fact, carbon is not even among the ten most abundant elements. Instead, it is merely one of the components making up the remaining 0.9% of Earth's crust. Why, then, do we pay this special attention to just one element from among 114?

The first reason is largely historical. In the early days of chemistry, scientists thought organic compounds were those produced by living organisms, and that inorganic compounds were those found in rocks and other nonliving matter. At the time, they believed that a "vital force," possessed only by living organisms, was necessary to produce organic compounds. In other words, chemists believed that they could not synthesize any organic compound starting with only inorganic compounds. This theory was very easy to disprove if, indeed, it was wrong: It required only one experiment in which an organic compound was made from inorganic compounds. In 1828, Friedrich Wohler (1800-1882) carried out such an experiment. He heated an aqueous solution of ammonium chloride and silver cyanate, both inorganic compounds and, to his surprise, obtained urea, an "organic" compound found in urine.

Although this single experiment of Wohler's sufficed to disprove the "doctrine of vital force," it took several years and a number of additional experiments for the entire scientific community to accept the fact that organic compounds could be produced in the laboratory. This discovery meant that the terms "organic" and "inorganic" no longer had their original meaning because, as Wohler demonstrated, organic compounds could be obtained from inorganic materials. A few years later, August Kekule (1829-

1896) put forth a new definition-organic compounds are those containing carbon-and his definition has been accepted ever since. A second reason for the study of carbon compounds as a separate discipline is the sheer number of organic compounds. Chemists have discovered or made more than 10 million of them, and an estimated 10,000 new ones are discovered or prepared in the laboratory each year. By comparison, chemists have discovered or made an estimated 1.7 million inorganic compounds. Thus approximately 85% of all known compounds are organic compounds

A third reasonand one particularly important for those of you who plan to study biochemistryis that carbohydrates, lipids, proteins, enzymes, nucleic acids (DNA and RNA), hormones, vitamins, and almost all other important chemicals in living systems are organic compounds. Furthermore, their reactions are often strikingly similar to those observed occurring in test tubes. For this reason, knowledge of organic chemistry is essential for an understanding of biochemistry. One final point about organic compounds. They generally differ from inorganic compounds in many of their properties, some of which are shown in Table 10.1. Most of these differences stem from the fact that the bonding in organic compounds is almost entirely covalent, while most inorganic compounds have ionic bonds. Of course, there are many exceptions to the generalizations in Table 10.1.Some organic compounds behave like inorganic compounds, and vice versa, but the generalizations remain largely true for the vast majority of compounds of both types.

Organic chemistry is the study of compounds containing carbon. o Chemists obtain organic compounds either by isolation from plant and animal sources or by synthesis in the laboratory. Carbon normally forms four bonds and has no unshared pairs of electrons. o Its four bonds may be four single bonds, two single bonds and one double bond, or one triple bond and one single bond. o Nitrogen normally forms three bonds and has one unshared pair of electrons. o Its bonds may be three single bonds, one single bond and one double bond, or one triple bond. o Oxygen normally forms two bonds and has two unshared pairs of electrons. o Its bonds may be two single bonds or one double bond. Functional groups are sites of chemical reactivity; a particular functional group, in whatever compound it is found, always undergoes the same types of reactions. In addition, functional groups are the characteristic structural units by which we both classify and name organic compounds. o Important functional groups include the hydroxyl group of 1o, 2o, and 3o alcohols; o the amino group of 1o, 2o, and 3o amines; o the carbonyl group of aldehydes and ketones; o and thecarboxyl group of carboxylic acids. ---- End of Lecture Summaries Series (#1)----