eee ees ear) eet Sra eae U Smo ec i eet aR] cree Cova Raney Srey Bary Se RES ae Paks Aad Sacre eT Deer "= Measuring K, for Acetic Acid Deemer ee aurea Eee Dt gee cue reel SSE Cues Prana Pee) Acids and Bases CeThe Nature of Chemical Equilibrium Key Terms sible ea ° al In systems that are in equilbrium, opposing processes occur at the same time and at the same rate. For example, when an excess of sugar is placed in water, some sugar molecules go into solution, and others remain undissolved. At equilibrium, molecules of sugar are crystalzing at the same rate that molecules trom the crystal are dissolving. The rate of evaporation ofa liquid in @ closed vessel can eventually tbe equaled by the rate of condensation of Its vanor. The resulting equilsrium vapor pressure is a characteristic ofthe liquid at the prevailing temperature. The preceding examples are physical equilibria. In this chapter, we will exeand on the pt of equilibrium to include chemical reactions. You wil learn how a system «at equilrium responds when equilibrium conditions are altered by ‘concentration, pressure, and temperature. @ main DEA All reactions are reversible under certain cond | Theoretically, every reaction can proceed in two directions, forward and reverse. Thus, essentially all chemical reactions are considered to be reversible under suitable conditions. A chemical reaction in which the products can react to re-form the reactants is called a reversible reaction. Mercury({} oxide decomposes when heated. 214g0(s) 2. 211g(0 + 0,18) Mercury and oxygen combine to form mercury(II) oxide when heated gently. 2Hg(I) + 0,(g) 4, 2Hg0(s) Figure 1.1 shows both of these reactions taking place. Suppose mercury(I) oxide is heated in a closed container from which neither the mercury nor the oxygen can escape. Once decomposition has begun, the mereury and oxygen released can recombine to form mercury(II) oxide again. Thus, both reactions can proceed at the same time. Under these conditions, the rate of the synthesis reaction will eventually equal that of the decomposi reaction. At equilibrium, mercury and oxygen will combine to form mercury(I) oxide at the same rate that mercury(II) oxide decomposes into mercury and oxygen. The amounts of mercury(I) oxide, mercury, and oxygen can then be expected to remain constant as long as these conditions persist: a state of dynamic equilibrium has been reached. SECTION 1 Des NE ee uae Rs Bee Cee eeu? Cee us FIGURE 1.1 Reversible Reactions with gethe reactions and iain the connection Chemical Equilibrium 563.© cuece Fon unpeRsTaNDING Explain The two terms dynamic and equim soem to conratict each ather at st. namic means that changes ae occuring, bt eauitium means that no overall change is happening. Given his explain vty the combination ofthe ‘we, nani equlibeum, i cortect. 564 Chapter 18 In sucha state of dynamic equilibrium, both reactions continue, but there is no net change in the composition of the system. A reversible ‘chemical reaction isin chemical equilibrium winen the rate ofits forward reaction equals the rate ofits reverse reaction and the concentrations ofits products and reactants remain unchanged. The chemical equation for the reaction at equilibrium is written using double arrows to indicate the overall reversibility of the reaction. i 2HgO(s) = 2Hg(0) + 0,(g) © Main WEA Some reactions favor products, and others reactants. ‘Many chemical reactions are reversible under ordinary conditions of ‘temperature and concentration. They will reach a state of equilibrium ‘unless at least one of the substances involved escapes or is removed from the reaction system. In some cases, however, the forward reaction is so predominant that essentially all reactants will react to form products. Here, the products of the forward reaction are favored, meaning that at equilibrium there is a much higher concentration of products than of reactants. Hence, we can say that the equilibrium “lies to the right,” because products predominate, and products conventionally are written on the right side of a chemical equation. An example of such a system is ‘the formation of sulfur trioxide from sulfur dioxide and oxygen. 280,(g) + 0,(g) = 250,66) Notice that the equation is written showing an inequality of the two arrow lengths. The forward reaction is represented by the longer arrow to imply that the product is favored in this reaction. In other cases, the forward reaction is barely under way when the rate of the reverse reaction becomes equal to that ofthe forward reaction, and equilibrium is established. In these cases, the amounts of reactants remain high, and the amounts of products are low. Here, we say that the equilibrium “lies to the left” because the reactants are the predominant species. An example of such a system is the acid-base reaction between carbonic acid and water. H,CO,(aq) + H,0(0 «=# H,0"(aq) + HCO} (aq) In still other cases, both forward and reverse reactions occur to nearly the same extent before chemical equilibrium is established. Neither reaction is favored, and considerable concentrations of both reactants and products are present at equilibrium. An example is the dissociation of sulfurous acid in water. H,$0,(aq) + H,0(0) = H,0*(aq) + HS03(aq) Chemical reactions ordinarily are used to convert available reactants into more desirable products. Chemists try to convert as much of these reactants as possible into products. The extent to which reactants are converted to products is indicated by the numerical value of the equilibrium constant, which will be described in the next section,@ main iweEA At equilibrium, the concentrations of reactants and products remain constant. Suppose two substances, A and B, react to form products Cand D. In turn, Cand D react to produce A and B. Under appropriate conditions, equilibrium occurs for this reversible reaction. This hypothetical equilib- rium reaction is described by the following general equation. nA + mB = xC +yD Initially, the concentrations of C and D are zero, and those of A and B are maximum. Figure 1.2 shows that, over time, the rate of the forward reaction decreases as A and B are used up. Meanwhile, the rate of the reverse reaction increases as C and D are formed. When these two reaction rates become equal, equilibrium is established. The individual concentrations of A, B, C, and D undergo no further change if conditions remain the same. Once equilibrium is attained, the concentrations of products and reactants remain constant, so a ratio of their concentrations should also remain constant. The ratio of the mathematical product (C}* x [DP’to the ‘mathematical product [A}" x [B]" for this reaction has a definite value at a given temperature. Itis the equilibrium constant of the reaction and is designated by the letter K. The following equation describes the equilib- rium constant for the hypothetical equilibrium system. The brackets ({ J) indicate the concentration of each substance as expressed in mol/L. The superscripts are the coefficients of each substance in the balanced chemical equation [ck(DP far(By" Equilibrium Constant K coon Rate Comparison forthe Reaction System Equilibrium Reaction AvBoG+D Systems Shown are reaction rates for the hypothetical equitvium reaction system A+B e200. From the tina Aand B are mined together tf the ate ofthe forwad reaction d nd the rae of the reverse reaction increases untl both and rovorse reaction rates are oqual when the equlrium condition begins. C+D A4B (reverse reaction) Equiosum (rward rate = reverse rate) Chemical Equilibrium 565CoE) Hy ly HI Equilibrium System Tho vio! ealar ofthe reactant indie gs, givs an ind cation ofthe progress ofthe reaction between hyrogen and iodine, Bath H,(eactan) and H 566 (product) ar Chapter 18 gases. The darker the ask, the less I, gas nts remain. ‘The concentrations of substances on the right side of the chemical equation appear in the numerator of the ratio, with each concentration raised to a power equal to the coefficient of that substance in the balanced chemical equation. These substances are the products of the forward reaction. The concentrations of substances on the left side of the chemical ‘equation are in the denominator of the ratio, with each concentration raised to a power equal to the coefficient of that substance in the balanced chemical equation. These substances are the reactants of the forward reaction. The constant K is independent of the initial concentrations. Itis, however, dependent on the temperature of the system. The Equilibrium Constant ‘The numerical value of K for a particular equilibrium system is obtained experimentally. The chemist must analyze the equilibrium mixture and determine the concentrations of all substances. The value of K for a given. equilibrium reaction at a given temperature shows the extent to which the reactants are converted into the products of the reaction. Ifthe value of Kis small, the forward reaction occurs only very slightly before ‘equilibrium is established, and the reactants are favored. A large value of K indicates an equilibrium in which the original reactants are largely converted to products. Only the concentrations of substances that can actually change are included in K. This means that pure solids and liquids are omitted, because their concentrations cannot change. In general, then, the equilibrium constant, K, is the ratio ofthe ‘mathematical product of the concentrations of substances formed at ‘equilibrium to the mathematical product of the concentrations of react- ing substances, Each concentration is raised to a power equal to the coefficient of that substance in the chemical equation. The ‘equation for Kis referred to as the chemical equilibrium expression. The H,, [, Hl Equilibrium System ‘An excellent example of an equilibrium system occurs with the reaction between H, and I, vapor in a sealed flask at an elevated temperature. A typical look at this reaction can be seen in. Figure 1.3, Ifthe reaction were observed, its rate could be followed by making note of how quickly the violet color of the iodine vapor diminished. Ifcolorless H, gas is present in excess, we might expect that the reaction would continue untill ofthe I, is used up. The violet color of the flask would decrease in intensity until all ofthe iodine reacts, At that time, the beaker would be color- less, because both HI and the excess HL, are colorless gases. In actuality, the color fades to a constant intensity but does not disappear completely, because the reaction is reversible. Once the reaction between H, and I, reaches a certain point, hydrogen iodide decomposes to re-form hydrogen and iodine. ‘The rate of this reverse reaction increases as the concentration of hydrogen iodide increases. ‘ou Stpenowenronetat