Challenge Derive the following results for a triprotic ac: Kua * Kos = Kw (6-38) Kas Kea = Ky 6-39) Kag* Ky = Ky (6-40) Shorthand for Organic Structures We are beginning 1 encounter organic (carbon-containing) compounds in this. book ‘Chemists and biochemists use simple conventions for drawing molecules to avoid writing ‘every atom. Each vertex of a structure is understood to be a carbon atom, unless otherwise labeled. Inthe shorthand, we usually omit bonds from carbon to hydrogen, Carbon forts fout chemical bonds. If you see earbon forming fewer than four bonds, the remaining bonds ae assumed to go to hydrogen atoms that are not written, Here isan example Dashed bond goes behind ‘he plane of the page Ieis understood that there Ho ‘ainasnat SH Wedge shows a bond Secon PO OF Conmgostoriicpine HQ fH wok ee aon ES ho x 7 AS “ cc oH, — Nn, —cH, P / 2 S,—cH Semen, Ct hs two equalentresrance chem NETO Stuctures, so all €~ Bonds are equivalent ae We often draw benzene rings witha circle in place of three double bonds. O- O ae Benzene Cy Terms to Understand acid acid dissociation constant (K,) acidic solution Bronsted-Lowry base ‘carboxylate anion carboxylic acid ‘common ion effect ammonium ion ‘complex ion aprotic solvent conjugate acid-base pair utoprotolysis, coprecipitation base ‘cumulative formation constant base hydrolysis constant (K,)__disproportionation, basic solution endothermic Bronsted-Lowry acid enthalpy change Epinephrine aso callod adresse) ‘Shorthand dawing of epinepbsine ‘The shorthand shows that the carbon atom at the top right of the six-membered benzene ring forms three bonds to other carbon atoms (one single bond and one double bond), so there must be a hydrogen atom attached to this carbon atom. The carbon ator atthe left side ofthe benzene ring forms three bonds to other carbon atoms and one bond to an oxygen atom. There is no hidden hydrogen atom attached to this carbon, In the CH, group adjacent to nitrogen, both hydrogen atoms are omitted in the shorthand structure. entropy overall formation constant equilibrium constant pH exothermic polyprotie acids Gibbs free energy polyprotic bases hydronium ion protic solvent ion pair reaction quotient Le Chatelier’s principle salt Lewis acid saturated solution Lewis base solubility product ligand standard state neutralization stepwise formation constant SUA ry For the reaction aA + 6B = cC + dD, the equilibrium constant is K = [C}(DIMAY"IB}". Solute concentrations should be expressed jn moles per liter; gas concentrations should be in bars; and the concentrations of pure solids, liquids, and solvents are omitted. 1f the direction of a reaction is changed, K" = /K. If two reactions, are added, K = KK. The equilibrium constant can be calculated from the free-energy change for a chemical reaction: K = e977, ‘The equation AG = AH = TAS summarizes the observations that a | ss reaction is favored if it liberates heat (exothermic, negative AH) or increases disorder (positive AS). Le Chatelier’s principle predicts the effect on a chemical reaction when reactants or products are added or temperature is changed. The reaction quotient, Q, tells how a system must change to reach equilibrium, ‘The solubility product is the equilibrium constant forthe disso- lution ofa solid salt into its constituent ions in aqueous solution. The common ion effect is the observation that, if one of the fons of that CHAPTER 6 Chemical Equilibriumsalt is already present in the solution, the solubility of a salt is de- creased, Sometimes, we can selectively precipitate one ion from a solution containing other ions by adding a suitable counterion. At high concentration of ligand, a precipitated metal ion may redissolve by forming soluble complex ions. In a metal-ion complex, the metal is a Lewis acid (electron pair acceptor) and the ligand is a Lewis base (electron pair donor). Bronsted-Lowry acids are proton donors, and Bronsted-Lowry bases are proton acceptors. An acid inereases the concentration of 1,0" in aqueous solution, and a base increases the concentration of OH’. An acid-base pair related through the gain or loss ofa single proton is described as conjugate. When a proton is transferred from ‘one molecule to another molecule of a protic solvent, the reaction is called autoprotolys ‘The definition pH = ~log(H™] will be modified to include activ- ty later, K, is the equilibrium constant for the dissociation of am avid: HA + HO = H,0* + A~. The base hydrolysis constant forthe reaction B+ HO = BH’ + OH” is Ky, When either K, or Ky is large, the acid or base is said to be strong; otherwise, the acid or base is weak. Common strong acids and bases are listed in Table 6-2, which you should memorize. The most common weak acids are carboxylic acids (RCO;H), and the most common weak bases are amines (R3N:). Carboxylate anions (RCOs) are weak bases, and ammonium ions (RjNH") are weak acids. Metal cations are weak acids. For a conjugate acid-base pair in water, K,-Ky = Ky. For polyprotic acids, we denote successive acid dissociation con- stants a8 Kyy, Kya. Kus. °~ of just Ky. Ka, Ks, ~~ For polybasic species, we denote successive hydrolysis constants Ki, Kias Kise Fora diprotic system, the relations between successive acid and base ‘equilibrium constants are Kay Kya = Ky and Kya*Kyy = Ky. For a twiprotic system, the relations are K,y*Kiy = Kus Kia" Koa = Ky and Kar Kut = Ky In the chemists’ shorthand for organic structures, each vertex is ‘carbon atom, If fewer than four bonds to that carbon are shown, itis understood that H atoms are attached to the carbon so that it makes four bonds, EXCTC5 C5 tnasrsssmemmomantscesiiann inks at A name 6-A. Consider the following equilibria in aqueous solution: (1) Agt + CI” = AgCi(ag) K=20% 10° (2) AgCKag) + CI” = Agcy K=93% 10! 3) AgCls) = Ag” + > K=18x 10" (a) Caleulate the numerical value of the equilibrium constant forthe reaction AgC\(s) = AgClaq). (b) Calculate the concentration of AgCl(ag) in equilibrium with excess undissolved solid AgCl (© Find the numerical value of K for the reaction AgCiz AgCls) + CI 6B. Reaction 6-7 is allowed to come to equilibrium in a solution initially containing 0.010 0M BrO3, 0.0100 M Cr°*, and 00M H*. ‘To find the concentrations at equilibrium, we can Construct a table showing initial and final concentrations (see below). We use the stoichiometry coeficients ofthe reaction to say that i x mol of Br are created, then we must xlso make x mol of Cr,03~ and 8x mol of H*. To produce x mol of Br’, we must have consumed x mol of BrO} and 2s mol of C2" (a) Write the equilibrium constant expression that you would use to solve for x to find the concentrations at equilibrium. Do not try to sole the equation. (b) Because K = 1 x 10!', we suppose that the reaction will go nearly “to completion.” That is, we expect both the concentration of Br- and Cr,03~ to be close to 0.005 00 M at equilibrium. (Why?) ‘Thats, x= 0,005 00 M, With this value of x, (H"] = 1.00 + 8 1.04 M and [BrO; ] = 0.010 0 — x = 0.005 0 M. However, we can- not say [CF"*] = 0,010 0 ~ 2x = 0, because there must be some ‘small concentration of Cr°* at equilibrium. Write [Cr'*] for the concentration of Cr** and solve for [Cr'*]. The limiting reagent in this example is Cr°*, The reaction uses up Cr°* before consuming Bros: BrOy + 2Ce* + 40 Inia concentration 0.0100 0.0100 Final concentration __0.0100-x 0.0100~2+ Exercises Br 6-C. Find [La] in the solution when excess solid lanthanum jodate, La(IO,),, is stirred with 0.050 M LilOs umtil the system reaches equilibrium. Assume that 05 from La(IO,); is negligible compared with 105 from LilOs, 6-D. Which will be more soluble (moles of metal dissolved per liter of sofution), Ba(IOs)2 (Kp = 1.5 % 10-*) or CaOy)o (Kp = 7.1 x 10°7)? Give an example of a chemical reaction that might ‘occur that would reverse the predicted solubilities 6-E. Fe(IM) precipitates from acidic solution by addition of OH~ to form Fe(OH),(s). At what concentration of OH” will (Fe(IID)] be reduced to 1.0 X 10-"° M? If Fe(I) is used instead, what concen- tration of OH will reduce [Fe(II] to 1.0 x 10"! M7 6-F. Is it possible to precipitate 99.05 of 0.010 M Ce™* by adding oxalate (C07) without precipitating 0.010 M Ca*? CaCO, Ky = 13 X 10°F CexC.0y)s Ky = 59 10-* 6-G. For a solution of Ni?* and ethylenediamine, the following equilibrium constants apply at 20°C: Ni* + HNCH,CH.NH,, = Ni(en)?* EByeseinine (atic) Ni(en)’* + en = Ni(en)3* Nifen)}* + en = Ni(en)} Calculate the concentration of free Ni in a solution prepared by tnixing 0.100 mot of en plus 1.00 ml. of 0.010 0 M Ni” and diluting to 1.00 L with dilute base (which keeps all the en in its unprotonated form. Assume that nearly all nickel is in the form Niten)}*, so {Nifen)}*] = 1.00 x 10" M, Caleuate the concentrations of Ni(en)’* and Ni(en)3* to verify that they are negligible in compari- son with Ni¢en)}*, log K, = 7.52 + co} + aH 1.00) r 100+ 8x 1376-H. If each compound is dissolved in water, will the solution be acidic, basic, or neutral?” (a) Na"Br (©) (CHyN*cr () Na*CH,COz «0 (CHYN* C)-co, (© Nuicr (2) FetNOvs (@) KPO, 6-1. Succinic acid dissociates in two steps: i] I x, Il i nolcy,ca,ton #& — notcu,cu,¢o- + * K, = 6.2 x 10-8 ° i t ® -occn,cu,co~ + Ky = 23 10° Cau Kg, and Kafr he following eactios qo aod “ovcn,ci,lo- + 1,0 noccn,ci,¢o- + o#- 7 in| HOCCH,CH,CO™ + H,0 2 HOCCH,CH,COH + OHM Prob lens, eee Equilibrium and Thermodynamics 6-1, To evaluate the equilibrium constant in Equation 6-2, we must express concentrations of solutes in mol, gases in bars, and omit Solids, guid, and solvents. Explain why. 6-2. Why do we say that the equilibrium constant for the reaction H,0 = H® + OH (or any other reaction) is dimensionless? 6-3. Explain the statement that predictions about the direction of a reaction based on Gibbs free energy or Le Chitelier’s principle are thermodynamic, not Kinetic (64. Write the expression for the equilibrium constant for each of the following reactions. Write the pressure of a gaseous molecule, Xyas Py (a) 3Ag* (aq) + PO} (aq) = AgsPO«(s) (b) CoH) + FOX) — 3H,O(1) + 6CO2L) For the reaction 2A(g) + B(ag) + 3C(J) = D(s) + 3E(g), the concentrations at equilibrium are found to be A: 28 X 10° Pa c 128M E: 36 x 10" Tor B: 1.2 107M D: 165M Find the numerical value of the equilibrium constant that would appear in a conventional table of equilibrium constants 6-6, From the equations HOCI = Ht + OCI” HOCI + OBr~ = HOBr + OCI K= 30x10 K=15 find the value of K for the reaction HOBr == H* + OBr™ |e 6-J. Histidine isa triprotie amino acid Goat NH He cn, Lo mf CO; i NH nc—cu,—£> f N NH ‘What i the value ofthe equilibrium constant for the reaction ee nec + HO = HC—cl Mh x, GK. (a) From Ke in Table 61, aleuate the pH of pre wae a O20 and aoe (b) For the reaction D,O = D* + OD", (p" OD 35x 10” at 25°C, In this equation, D stands for deuterium, which is the isotope *H, What is the pD (= —log[D*)) for neutral D0? OS on % 6-7. (a) A favorable entropy change occurs when AS is. positive ‘Doss the order of the system inerease or decrease when AS is positive? (b) A favorable enthalpy change occurs when AH is negative. Does the system absorb heat or give off heat when AM is negative? (c) Write the relation between AG, AH, and AS. Use the results of parts (a) and (b) to state whether AG must be positive or negative for a spontaneous change. 6-8, For the reaction HCO; = H* + CO}, AG" = +59.0k0/mol at 298.15 K. Find the value of K for the reaction. 6-9, The formation of tetrafluoroethylene from its elements is highly exothermic: 2FAg) + 2Cls) = FC=CFa(2) Fuoine Gtupite "—‘Tevaftoretiyene (a) Ifa mixture of F, graphite, and CF, is at equilibrium in a closed container, will the reaction go (othe right o tothe left if Fis added? (b) Rare bacteria from the planet Teflon eat C;F, and make Teflon for their cell walls. Will the reaction go to the right orto the left if these bacteria are added? FF EF HWY x SAAASE sam ey aah oy #oehee (©) Will the reaction go right or left if solid graphite is added’? (Neglect any effect of increased pressure due to the decreased volume in the vessel when solid is added.) CHAPTER 6 Chemical Equilibrium(@) Will the reaction go right or left if the container is crushed to one-eighth ofits original volume? {) Does the equilibrium constant become larger or smaller if the container is heated? 61 BaCly-H,0(s) loses water when itis heated in an oven: BuCly-HsO(s) = BaCh(s) + H:0(8) AH? = 63.11 kifmol at 25°C 9° = $148 JAK + mol) at 25°C {@) Write the equilibrium constant for this reaction, Calculate the vapor pressure of gaseous 11,0 (Py) above BuCly*H,0 at 298 K. (b) IFAM and AS° are not temperature dependent (a poor assump- Sion), estimate the temperature at which Pj, above BaCly-H;0(3) willbe 1 bar. G11. The equilibrium constant for the reaction of NHs(aq) + H,0 = NH + OH” is K, = 1479 X 10-Sat Cand 1.570 x 10" 10°C. (a) Assuming AH" and AS are constant in the interval 510°C (grobbly good assumption for small AT), use Equation 68 wo find AH forthe reaction inthis temperature range {b) Describe how Equation 6-8 could be used to make a linear ‘graph to determine AH" if AH? and AS were constant over some perature range. G12, For Hy(g) + Bro(g) = 2HBr(g), K'= 7.2 X 10° at 1362 K tad AIP is postive. A ves is charged with 48.0 Pa HBr, 1 370 Pa Hs, and3 310 Pa Bry at 1 362 K. {@) Will the reaction proceed to the left or the right to reach equilibrium? {b) Calculate the pressure (in pascal) of each species inthe vessel. ateqlibrium. (c) I the mixture at equilibrium is compressed to half of its original une, wll the reaction proceed tothe left or the right to reestablish librium? () Ifthe mixture at equilibrium is heated from 1 362 0 1407 K, will be formed or consumed in order o reestablish equilibrium? 13. Henry’s law states thatthe concentration of a gas dissolved in liquid is proportional to the pressure of the gas. This law is a con- uence of the equilibrium _oI Px K, scaled the Henrys law constant. (The same law applies to solvents, bt the vale of Ks ifferent foreach solvent.) For the line additive MTBE, K, = 1-71 Mibur. Suppose we havea closed ‘vith aqueous sottion and air n equilibrium. Ifthe concen- of MTBE in the water is 1.00 x 10 ppm (= 100 wg MTBE/g tion ~ 100 jm), what sth pressure of MTBE in the sic? CH;—O—C(CH)s Ky X(g) + X(ag) Ky Metiy--buylthe (TBE, FM 88.15) 14) Find the concentration of Cu in equilibrium with CuBr(s) 15, What concentration of Fe(CN)$™ (ferrocyanide) is in equilib- 1 with 1.0 wM Ag* and Ag,Fe(CN)«(s). Express your answer ith a prefix from Table 1-3 lems 6-16, Find {Cu?*] in a solution saturated with Cus(OH)«(SO3) if {OH is fixed at 1.0 % 10° M, Note that Cuy(OH).(SO.) gives | mol of $0; for-4 mol of Cu?* Cu,(OH).(SO4)(5) = 4Cu?* + 6OH™ + SOF Ky = 23 X10? 6-17. (a) From the solubility product of zinc. ferrocyanide, Zn,Fe(CN)o, calculate the concentration of Fe(CN)g~ in 0.10 mM ZnSO, saturated with Zn;Fe(CN)s. Assume that ZnaFe(CN). is a negligible source of Zn” (b)_ What concentration of K,Fe(CN). should be in a suspension of solid Zn,Fe(CN). in water to give [Zn?"] = 5.0 x 10-7 M? 6-18. Solubility products predict that cation A?* ean be 99.99% separated from cation B?* by precipitation with anion X~. When the separation is tried, we find 0.2% contamination of AXs(s) with B?*. Explain what might be happening. 6-19. A solution contains 0,050 0 M Ca?” and 0.030 0M Ag*. Can 99% of Ca? be precipitated by sulfate, without precipitating Ag"? ‘What will be the concentration of Ca** when Ag:SO, begins to precipitate? 6-20, A solution contains 0,010 M Ba?” and 0.010 M_Ag*. Can 99.90% of either ion be precipitated by chromate (CrO}~) without precipitating the other metal ion? 6-21, If a solution containing 0.10 M Cl”, Br’, I~, and CrO2~ is treated with Ag”, in what order will the anions precipitate? Complex Formation 6-22. Explain why the total solubility of lead in Figure 6-3 first de- creases and then inereases as [I] increases, Give an example of the chemistry in each of the two domains. 6-28. dentfy the Lewis acids inthe following reactions: (@) BF, + NHy = FB—NH, (b) Fo ASE, = ASF 6-24. The cumulative formation constant for SnCh(ag) in 1.0 M. NaNO, is By = 12, Find the concentration of SnCl(aq) for asolu- tion in which the concentrations of Sn* and Cl” are both somehow fixed at 0.20 M. 6-25. Given the following equilibria, calculate the concentration of each zine species in a solution saturated with Zn(OH)3(3) and con- taining [OH] ata fixed concentration of 3.2 10-7 M, ZHOW)9) Ky = 3X 10°" Zn(OH)™ Bi = 1x 10% ‘Za(OH) (aq) By =2x 10° ‘Zn(OH)3 By = 8 x 107 Zn(0HK By = 3 x 10° 6-26. Although KOH, RDOH, and CsOH have little association between metal and hydroxide in aqueous solution, Liv and Na* do form complexes with OH” {LiOH(ag)) (Li7 0H] 020 Lit + OH” = LiOH(ag) Ky Nat + OH” = NaOH(ag) Ki Prepare a table like the one in Exercise 6-B showing initial and final concentrations of Na*, OH”, and NaOH(aq) in 1 F NaOH ssfsolution. Calculate the fraction of sodium in the form NaOH(aq) at equilibrium, 6-27. In Figure 6-3, the concentration of Pbfy(ag) is independent of [I]. Use any ofthe equilibrium constants for Reactions 6-11 through 6-15 to find the equilibrium constant for the reaction PDIx(s) = Phl:(aq), which is equal to the concentration of PbIs(aq) Acids and Bases 6-28, Distinguish Lewis acids and bases from Bronsted-Lowry acids and bases. Give an example of each, 6-29, Fill in the blanks: (a) The product of a reaction between a Lewis acid and a Lewis (b) The bond between a Lewis acid and a Lewis base is called (©) Bronsted-Lowry acids and bases related by gain or loss of one proton are said to be (a) A solution is acidic if A solution is basie if 6-30, Why is the pH of distilled water usually <7? How ean you prevent this from happening? 6-31, Gaseous $0 is ereated by combustion of sulfur-containing fuels, especially coal. Explain how SO; in the atmosphere makes acidic rain 6-32, Use electron dot structures to show why tetramethylammonium hydroxide, (CH3),N* OH is an ionic compound. That is, show why hydroxide is not covalently bound to the rest of the molecule. 6-33. Identify the Bronsted-Lowry acids among the reactants in the following reactions: (a) KCN + HI = HCN + KI (b) POS +H, HPO” + OH 6-34, Write the autoprotolysis reaction of H»SO,, 16-35, Identify the conjugate acid-base pairs in the following reac~ tions CO TSCILCHLSH, 1,0 —LALC © Opcon + Gy = O-co; + Qu" Pyedine Benzoate Pysitiniom Hy + H,O* Benzoie acid pH (6-36, Calculate [H"] and pH for the following solutions: (a) 0.010 M HNOs (@)3.0M HCI (b) 0.035 M KOH (©) 0.010 M ((CHs),N*]OH~ (©) 0.030 M HCI “Texanethylanoniam hydroxide 6-37. Use Table 6-1 t0 calculate the pH of pure water at (a) 25°C and (b) 100°C, 6-38, ‘The equilibrium constant forthe reaction H,O = H” + OH is 10 X 10” at 25°C. What is the value of K for the reaction 4H,O = 4H* + 40H? 6-39.) An acidic solution containing 0.010 M La” is treated with NaOH until La(OH); precipitates. At what pH does this occur? 6-40, Use Le Chitelier’s principle and Ky in Table 6-1 to decide ‘whether the autoprotolysis of water is endothermic or exothermic at (a) 25°C; (b) 100°C; (e) 300°C. 140 Strengths of Acids and Bases 6-41. Make a list of the common strong acids and strong bases ‘Memorize this list. (6-42, Write the formulas and names for three classes of weak acids and two classes of weak bases 6-43. Write the K, reaction for trichloroacetic acid, Cl,CCO3H, foe anilinium fon, (S)—NHy and for lanthanum ion, La** 6-44. Write the Ky reactions for pyridine and for sodium 2-mereap toethanol © Pyridine HOCH,CH,§:~ Na* Sain 2mereaptoethana 16-45, Write the K, and Ki, reactions of NaHCO, 16-46, Write the stepwise acid-base reactions for the following ions in water. Write the correct symbol (For example, Ky) for the equi- librium constant for each reaction. (a) HaNCH,CHNHy ® 0 0 "Eplenediamnonium fon To ~OCCH,CO Matonate fon 6-87, Which is a stronger acid, (a) or (b)? (a) ° ) ° CL,HCCOH ClH,CCOH Dichloroacetic acid Chloroacetic acid Ka8x 10> K.= 136% 10" Which is a stronger base, (e) or (4)? (© H.NNH, @ ° yang 1) Kote" HNCNH, Urea a 1S 10! 6-48, Write the Ki, reaction of CN. Given that the K, value for HCN is 6.2 10", calculate Ki for CN™ 6-49, Write the K,z reaction of phosphoric acid (HsPO,) and the Ky reaction of disodium oxalate (Na;C209). (6-50, From the Ki, values for phosphate in Equations 6-32 through 6-34, calculate the three K,, values of phosphoric acd. 6-51. From the following equilibrium constants, calculate the equi librium constant for the reaction HO;CCO,H = 2H* + C02 00 90 {UL . th HOCCOH = H* + HOCCO™ Oxalc acid 00 00 til roeeall!) Hocco” = HY + “ocCo™ Oval 6-52. (a) Using only Ky from Table 6-3, calculate how many | moles of Ca(OH), will dissolve in 1.00 L of water. (b) How will the solubility calculated in part (a) be affected by the K, reaction in Table 6-3? CHAPTER 6 Chemical EquilibriumThe planet Aragonose (Which is made mostly of the mineral nite, whose composition is CaCO) has an atmosphere containing and carbon dioxide, each ata pressure of 0.10 bar. The oceans strated with aragonite and have a concentration of H* equal 10 8 X 10-7 M, Given the following equilibria, calculate how many of calcium are contained in 2.00 L. of Aragonose seawater (5, aragonite) = Ca?*(aq) + CO}(ag) Key = 6.0% 10-2 COX) = COx(ag) Keo, = 34x 107 00,(ag) + HzO(1) = HCO; (ag) + H*(ag) Ky 5x 10-7 HCOs (aq) = H*(aq) + CO}(ag) Ky = 4.7.x 107" 'tpanic! Reverse the first reaction, add all the reactions together, see what cancels.