0 Electrochemistry Oxidation-Reduction Reactions 20.4 202 20.3 20.4 20.5 206 @ (o) © @ ©) © Oxidation is the loss of electrons. ‘The electrons appear on the products side (right side) of an oxidation half-reaction. ‘The oxidant is the reactant that is reduced; it gains the electrons that are lost by the ‘substance being oxidized. Reduction is the gain of electrons, ‘The electrons appear on the reactants side (left side) of a reduction halt-reaction. ‘The reductantis the reactant that is oxidized; it provides the electrons that are gained by the substance being reduced Analyze/Pian. Given a chemical equation, we are asked to indicate which elements undergo a change in oxidation number and the magnitude of the change. Assign oxidation numbers according to the rules given in Section 4.4, Note the changes and report the magnitudes. Solve: fa) (b) © (@) @ (b) © @ Tis reduced from +5 to 0; Cis oxidized from +2 to +4. Hg is reduced from +2 to 0; Nis oxidized from -2 to 0. Nis reduced from +5 to +2; S is oxidized from -2 to 0. Clis reduced from +4 to +3; 0 is oxidized from -1 to 0. No oxidation-reduction is oxidized from -1 to +5; Cl is reduced from +1 to -1 Sis oxidized from +4 to +6; N is reduced from +5 to +2. ‘Sis reduced from +6 to +4; .Br is oxidized from -1 to 0. ‘Analyze/Plan. Write the balanced chemical equation and assign oxidation numbers. The substance oxidized is the reductant and the substance reduced is the oxidant. Solve: @ (b) @) (o) TiCl(g) + 2Mg(l) > Ti(s) + 2MgCI,(0) Ma()) is the reductant; TiCl,(g) is the oxidant. 2N,H,(g) + N,O,(g) > 3N,(g) + 4H,0(9) N,O, serves as the oxidizing agent; itis itself reduced. NH, serves as the reducing agent: itis itself oxidized 51420 Electrochemistry Solutions to Exercises 20.7 208 209 Analyze/Plan. Follow the logic in Sample Exercises 20.2 and 20.3. If the half-reaction occurs in basic solution, balance as in acid, then add OH" to each side. Solve: (2) Sn*(aq) > Sn“(aq) + 2e", oxidation (b) —TiO,(s) + 4H"(aq) + 2e" > T#*(aq) + 2H,0(0), reduction (©) ClO;(aq) + 6H(aq) + Be" > Cr(aq) + 3H,0(), reduction (6) 40#(aq) > 0,(g) + 2H,0()) + 4e°, oxidation (e) $0,*(aq) + 20#(aq) > S0(aq) + H,0(1) + 26°, oxidation (2) Mo™(aq) + 3e > Mo(s), reduction (b) —_H,SO,(aq) + H,0(!) > SO,*(aq) + 4H’(aq) + 2e", oxidation (€) _NO,-(aq) + 4H"(aq) + 3e- > NO(g) + 2H,0(1), reduction (2) Mn*(aq) + 40H"(aq) > MnO,(s) + 2H,0(|) + 2e", oxidation (e) _ Cr(OH),(s) + SOH(aq) > CrO,* (aq) + 4H,0(!) + 3e°, oxidation Analyze/Pian. Follow the logic in Sample Exercises 20.2 and 20.3 to balance the given equations. Use the method in Sample Exercise 20.1 to identify oxidizing and reducing agents. Solve: (2) Cr,0;*(aq) + Faq) + 8H* > 2CP*(aq) + 10,-(aq) + 4H,0(1) oxidizing agent, Cr,0;7-; reducing agent, I> (b) The half-reactions are: ‘4[MnO, (aq) + 8H"(aq) + Se" > Mn*(aq) + 4H,0(!)] SICH,OH(aq) + H,0() > HCO,H(aq) + 4H"(aq) + 4e71 4Mn0,(aq) + SCH,OH(aq) + 12H"(aq) > 4Mn*(aq) + SHCO,H(aq) + 11H,0() oxidizing agent, MnO, reducing agent, CH,OH © Ls) + 6H,0() > 210; (aq) + 12H"(aq) + 10¢" ‘S{OCr (aq) + 2H"(aq) + Ze" > Cr(aq) + H,0(1)] 1s) + 50Ct (aq) + H,0()) > 210," (aq) + SC + 2H*(aq)] ‘oxidizing agent, OCI; reducing agent, I, @ As,0;(8) + 5H,O(!) > 2H,AsO,(aq) + 4H"(aq) + 4e- 2NO; (aq) + 6H"(aq) + 4e” > N,O,(aq) + 3H,0(!) AAs,0,(6) + 2NO, (aq) + 2H,0() + 2H'(aq) > 2H,ASO (ag) + N,03(aq) oxidizing agent, NO,-; reducing agent, As,O, 51520 Electrochemistry Solutions to Exercises 20.10 (e) @ Net: () © 2[MnO, (aq) + 2H,O(!) + 3e” - MnO,{s) + 40H] Br (aq) + GOH (aq) > BrO,"(aq) + 3H,O(!) + 6e- 2MnO, (aq) + Br (aq) + H,O(1) > 2MnO,(s) + BrO," (aq) + 20H'(aq) ‘oxidizing agent, MnO,"; reducing agent, Br- Pb(OH),*(aq) + ClO(aq) > PbO.(s) + Cr(aq) + 20H"(aq) + H,O(!) oxidizing agent, CIO" ; reducting agent, Pb(OH),- 3{NO;"(aq) + H,0(1) > NO,(aq) + 2H"(aq) + 267 Cr,0;*(aq) + 14H"(aq) + Ge" > 2Cr*(aq) + 7H,O(!) 3NO,"(aq) + Cr,0,*(aq) + 8H"(aq) > 3NO,-(aq) + 2C?*"(aq) + 4H, 0(1) oxidizing agent, Cr,0,*; reducing agent, NO,- 4IAs(s) + 3H,O(1) > HAsO,(aq) + 3H"(aq) + 36°] 3{C10,- (aq) + SH"(aq) + 4e- > HCIO(aq) + 2H,0()] 4As(8) + 3C10,"(aq) + 6H,O()) + 3H"(aq) > 4H,AsO,(aq) + 3HCIO(aq) oxidizing agent, CIO,"; reducing agent, As 21Cr,0,* (aq) + 14H" (aq) + 66" > 2C*(aq) + 7H,0(D] 3{CH,OH(aq) + H,0() > HCO.H(aq) + 4H"(aq) + 464] 2Cr,0;* (aq) + 3CH,OH(aq) + 18H"(aq) > 4Cr"(aq) + 3HCO,H(aq) + 11H,0() ‘oxidizing agent, Cr,0;*; reducing agent, CH,OH 2[Mn0,"(aq) + 8H"(aq) + Se~ > Mn™*(aq) + 4H,0(1)) S(2Cr(aq) > Ch(aq) + 267 2MnO,-(aq) + 10Cr(aq) + 18H"(aq) > 2Mn*(aq) + SCL(g) + 8H,0(1) ‘oxidizing agent, MnO,"; reducing agent, Cr H,0,(aq) + 2e" > 0,(g) + 2H'(eq) Since the reaction is in base, the H’ can be “neutralized” by adding 20H” to each side of the equation to give H,O,(aq) + 20H"(aq) > 0,(g) + 2H,0() + 2e" ‘The other haif reaction is 2[CIO,(aq) + &- > ClO; (aq)}. H,0,{aq) + 2CI0,(aq) + 20H(aq) > O,(g) + 2CI0,“(aq) + 2H,O(1) ‘oxidizing agent, CiO,; reducing agent, H,0, 4{H,0,(aq) + 20H (aq) > 0,(g) + 2H,0(1 + 2e7] C10, (aq) + 3H,O() + Be" > 2C10,"(aq) + 6OH (aq) C1,0,(aq) + 4H,0,(aq) + 20H"(aq) > 2CI0,-(aq) + 40,(g) + 5H,0() ‘oxidizing agent, Cl,0,; reducing agent, H,O, 5162 0 Electrochemistry Solutions to Exercises Voltaic Cells; Cell Potential 20.11 (a) (b) 20.12 (a) () The reaction Cu*(aq) + Zn(s) > Cu(s) + Zn*(aq) is occurring in both Figures. In Figure 20.3, the reactants are in contact, and the concentrations of the ions in solution aren't specified. In Figure 20.4, the oxidation hait-reaction and reduction halt- reaction are occurring in separate compartments, joined by a porous connector. The concentrations of the two solutions are initially 1.0 M. In Figure 20.4, electrical current is isolated and flows through the voltmeter. In Figure 20.3, the flow of electrons cannot be isolated or utilized. In the cathode compartment of the voltaic cell in Figure 20.5, Cu**cations are reduced to Cu atoms, decreasing the number of positively charged particles in the compartment. Na” cations are drawn into the compartment to maintain charge balance as Cu** ions are removed. ‘The porous glass dish in Figure 20.4 provides a mechanism by which ions not directly involved in the redox reaction can migrate into the anode and cathode compartments to maintain charge neutrality of the solutions. Ionic conduction within the cell, through the glass disk, completes the cell circuit. In the anode compartment of Figure 20.5, Zn atoms are oxidized to Zn* cations, increasing the number of positively charged particles in the compartment. NO,” anions. migrate into the compartment to maintain charge balance as Zn** ions are produced. 20.13 Analyze/Plan. Follow the logic in Sample Exercise 20.4. Solve: @ & © @ © 20.14 (a) @) © ® (C) 20.15 (a) (b) Ag’(aq) + 1e° > Ag(s); Fe(s) > Fe*(aq) + 2e- Fe(s) is the anode, Ag(s) is the cathode. Fe(s) is negative; Ag(s) is positive. Electrons flow from the Fe(-) electrode toward the Ag(+) electrode. Cations migrate toward the Ag(s) cathode; anions migrate toward the Fe(s) anode. Alls) > AP*(aq) + 3e7; N?*(aq) + 26° > Ni(s) ‘Ai(s) is the anode; Nis) is the cathode. A\(s) is negative (-); Ni(s) is positive (+). Electrons flow from the Al(-) electrode toward the Ni(+) electrode. Cations migrate toward the Ni(s) cathode; anions migrate toward the Al(s) anode. Electromotive force, emf, is the driving force that causes electrons to flow through the extemal circuit of a voltaic cell. It is the potential energy difference between an electron at the anode and an electron at the cathode. (One voltis the potential energy difference required to impart 1 J of energy toa charge of 1 coulomb. 1V= 1 IC. 51720 Electrochemistry Solutions to Exercises () 20.16 (a) (b) (©) 20.17 (a) (b) (©) 20.18 (a) (o) «© 20.19 (a) (b) (©) Coll potential, E..,, is the emf of an electrochemical cell. ‘The Zn electrode, the anode, on the right of figure 20.4 has the higher potential energy for electrons. ‘The units of electrical potential are volts. A potential of one volt imparts one joule of energy to one coulomb of charge. A standard cell potential describes the potential of an electrochemical cell where all components are present at standard conditions: elements in their standard states, gases at 1 atm pressure and 1 M aqueous solutions. 2H’(aq) + 2e° > H.(9) A standard hydrogen electrode is a hydrogen electrode where the components are at standard conditions, 1 MH*(aq) and H,(g) at 1 atm. ‘The platinum foil in an SHE serves as an inert electron carrier and a Solid reaction surface. H,(g) > 2H*(aq) + 2e- The platinum electrode serves as a reaction surface; the greater the surface area, the more H, or H* that can be adsorbed onto the surface to facilitate the flow of electrons. A standard reduction potential ‘is the relative potential of a reduction half-reaction ‘measured at standard conditions, 1 M aqueous solutions and 1 atm gas pressure. Eq 7 0 V for a standard hydrogen electrode. ‘The reduction of Ag"(aq) to Ag(s) is much more energetically favorable, because ithas substantially more positive E,_., (0.799 V) than the reduction of Sn*(aq) to Sni(s) (-0.136 V). 51820 Electrochemistry Solutions to Exercises 20.20 (a) __Itisnot possible to measure the standard reduction potential of a single half-reaction because each voltaic cell consists of two half-reactions and only the potential of a complete cell can be measured. (b) The standard reduction potential of a half-reaction is determined by combining it wth a reference hatf-reaction of known potential and measuring the cell potential. ‘Assuming the half-reaction of interest is the reduction half-reaction: E coy = E pag (Cathode) - E, (anode) = E,. ,(unknown) - E,, (reference); E,,,(unknown) = E., +E,_, (reference). (©) Cd*(aq) + 2e° 9 Cals) E° = -0.403V Ca*(aq) + 2e" > Cals) E*=-2.87V The reduction of Ca"(aq) to Ca(s) is the more energetically unfavorable reduction because it has a more negative E° value. 2021 Analyze/Plan. Follow the logic in Sample Exercise 20.5. Solve: (2) The two half-reactions are: TP(aq) + 2e" > TI'(aq) cathode E,, 21CP*(aq) > Cr*(aq) +e] anode E,., 2 041 () =E,,, (cathode) -E,,, (anode); 119V=E,., - (-0.41 V); =1.19V-0.41V=0.78V © = (= 7 Anode (-) Cathode (+) Inert Inert Electrode (Pt) Salt Electrode (Pt) Bridge Solution Contains anions Solution Contains (00), Ot Sion: " 3% Cr*(aq), Cr*(aq) cations TV'(aq), TI*"(eq) Note that because Cr*(aq) is readily oxidized, it would be necessary to keep oxygen out of the left-hand cell compartment. 2022 (a) — PACI,*(aq) + 2e" > Pd(s) + 4Cr cathode E,,., =? ‘Cd(s) > Cd*(aq) + 26° anode Eig =0.403V (©) Ey =E gq (Cathode) -E,,., (anode); 1.03 V=E,., - (-0.403 V); E,, = 1.03 V-0.403 = 0.63V 5192 0 Electrochemistry Solutions to Exercises (o) Anode (-) Cd San Bridge Solution Contains anions goons, Coton) cations ~. Cathode (+) Pd Solution Contains PdClq?(aq), CI"(aq) 20.23 Analyze/Plan. Follow the logic in Sample Exercise 20.8. Solve: a) Cl(g) > 2Cr(aq) + 26° Ls) + 2e" > 2I(aq) E* =1.359 V- 0.536 V=0.823V (b) Ni(s) > N?*(aq) + 2e- 2[Ce(aq) + 1e° > Ce*(aq)] * = 1.61 V-(-0.28 V) = 1.89V © Fe(s) > Fe*(aq) + 20" 2[Fe*(aq) + 1e” > Fe*(aq)] E* = 0.771 V-(-0.440V)= 1.211 @ 3{Ca(s) > Ca*(aq) +27] 2[AP*(aq) + 3e” > Al(s)] E* = -1.66 V - (-2.87 V)] =1.21V 20.24 (a) —_F,(g) + 26° > 2F-(aq) H,(g) > 2H"(aq) + 26" E* =2.87V-0.00V=287V (b) Cu(s) > Cu*(aq) + 2e- Ba*(aq) + 26° > Ba(s) E* =-2.90V- (0.337 V) =-324V (©) Fe*(aq)+2e" > Fes) 2[Fe*(aq) > Fe™(aq) + 1¢] E*=-0.440V-O.771V=-1.211V (@) Hg.""(aq) + 2e” > 2Ha() 2[Cu'(aq) > Cu*(aq) + te] E° =0.789 V - 0.153 V = 0.636 V 520 Egg 7 1950 Eg = 0.536V E24 =0.789V E og 0-15320 Electrochemistry Solutions to Exercises 20.25 20.26 2027 Analyze/Plan. Given four half-reactions, find E,_., from Appendix E and combine them to obtain a desired E.,,. (a) The largest E.,, will combine the half-reaction with the most positive E,,,4 8 the cathode reaction and the one with the most negative E.., as the anode reaction. (b) The smallest positive E ..., will combine two half-reactions whose E, ., values are closest in magnitude and sign. Solve: (2) 3tAg"(aq) + 1€° > Ag(s)} E,., = 0.798 Crs) > Cr*(aq) + Se" E sog 70-74 3Ag’(aq) + Cris) > 3Ag(s)+Cr“(aq) - E* = 0.799 - (-0.74) = 1.54V (b) Two of the combinations have essentially equal E* values. 21Ag"(aq) + 1e- > Ag(s)] E og = 0.700V Culs) > Cu(aq)+2e —E, = 0.337 2Ag"(aq) + Cus) > 2Ag(s) + Cu*(aq) E° = 0.799 V - 0.337 V= 0.462 V 3[N#*(aq) + 2e" > Ni(s)] Ena =0.28V 21CK(s) > Cr*(aq) + 36°) Eg = 0.74V 3NF*(aq) + 2Cr(s) > 3t s) + 20*(aq) E* = -0.28V-(-0.74 V) = 0.46 V @ 21Au(s) + 4Br(aq) > AuBry(aq)+3e] ——E,,, = -0.858 V Bie" +10" (aq) + H,01) > Taq) + 20H (agi) E,,4= 0.49V 2Auls) + BBr (aq) + 31O-(aq) + 3H,O() > 2AuBr, (aq) + 3T(aq) + 6OH (aq) E* = 0.49 - (-0.858) = 1.35 V () 2[Eu*(aq) > Eu™(aq) + 1€7] Eg = -043V ‘Sn*(aq) + 2e” > Snis) E og =-0.14V 2Eu*(aq) + Sn*(aq) -> 2Eu*(aq) + Sn(s) E* = 0.14 (0.43) =0.29V Analyze/Plan. follow the logic in Sample Exercise 20.7. Solve: (2) MnO,-(aq) + 8H*(aq) + Se” > Mn*(aq) + 4H,0() E,,, = 1.51V (b) Because the half-reaction in part ( reaction. the more favorable reduction, itis the cathode (©) Sn*(aq) > Sn*(aq) + 2e° E,., = 0.154V (4) _ Balance electrons by multiplying the cathode reaction by 2 and the anode reaction by5. 5Sn*(aq) + 2Mn0, (aq) + 16H"(aq) > 5Sn“(aq) + 2Mn**(aq) + BH,0(1) 52120 Electrochemistry Solutions to Exercises 20.28 20.29 20.30 (e) E°= 1.61 V-0.154.V = 1.356 = 1.36 V (2) The halt-reactions are: 2H"(aq) + 2e" > HA9) Alls) > AP*(aq) + 3e- Because it has the larger E,,., (0.00 V vs -1.66 V), the first half-reaction is the reduction half-reaction in a voltaic cell. The standard hydrogen electrode (SHE) is the cathode and the Al strip is the anode. (©) The A strip will lose mass as the reaction proceeds, because Al(s) is transformed to AP*(aq). (©) Balance electrons by multiplying the cathode reaction by 3 and the anode reaction by2. 6H’(aq) + 2A\(s) > 3H,(g) + 2AF*(aq) () —- E*=0.00V-(-1.68V) = 1.66 V Analyze/Plan. Given the description of a voltaic cell, answer questions about this cell. Combine ideas in Sample Exercises 20.4 and 20.7. The reduction half-reactions are: Cu*(aq) +e" > Cu(s) E°= 0.337V ‘Sn*(aq) +2e" > Sn(s) E*=-0.136V Its evident that Cu** is more readily reduced. Therefore, Cu serves as the cathode, Sn as the anode. (b) The copper electrode gains mass as Cu is plated out, the Sn electrode loses mass ‘as Sn is oxidized. (©) The overall cell reaction is Cu(aq) + Sn(s) > Cu(s) + Sn*(aq) () — E*= 0.337 V-(-0.136 V)=0.473V (a) ‘The two half-reactions are: Pb#(aq) +26” > Pbis) E*=.0.126V L(g) +2e° > 2Cr(aq) —E” = 1.359 Because E* for the reduction of Cl, is higher, the reduction of Cl, occurs at the Pt cathode. The Pb electrode is the anode. (v) The Pb anode loses mass as Pb™(aq) is produced. (©) Chg) + Pb(s) > Pb*(aq) + 2Cr (aq) (@)—-E=1.359V-(-0.126 VY) = 1.485 52220 Electrochemistry Solutions to Exercises Oxidizing and Reducing Agents; Spontaneity 2031 20.32 20.33 20.34 20.35 20.36 ‘Analyze/Pian. Use the definitions of oxidizing agent, reducing agent and the convention for writing reduction half-reactions to answer the stated questions. Solve: (2) Negative. A strong reductant is likely to be oxidized, thus having a negative reduction potential (&) Right. Reducing agents are likely to be oxidized, and thus to be in a low oxidation state; the products of reduction half-reactions are in lower oxidation states than reactants. (2) Top. The reduction haif-reactions near the top of Table 20.1 are most likely to occur, a strong oxidant is most likely to be reduced (>) Left. An oxidant is reduced, so it is a reactant in a reduction haif-reaction. Analyze/Plan. Follow the logic in Sample Exercise 20.8. In each case, choose the half- reaction with the more positive reduction potential and with the given substance on the left. Solve: (a) CL{g) (1.359 V vs. 1.065 V) (b) Ni*(aq) (-0.28V vs. -0.403 V) (©) BrO, (aq) (1.52 Vvs. 1.195 V) (6) 0,(g) (2.07 Vvs. 1.776) ‘The more readily a substance is oxidized, the stronger it is as a reducing agent. In each case choose the half-reaction with the more negative reduction potential and the given substance ‘on the right. (a) Mo(s) (-2.37 Vvs. -0.44 V) (b) Cals) (-2.87 V vs. -1.66 V) (©) Hg, acidic) (0.000 V vs. 0.141 V) (4) H,C,0,(aq) (-0.49 V vs. 0.17 V) Analyze/Plan. If the substance is on the left of a reduction half-reaction, it will be an oxidant; if itis on the right, it will be a reductant. The sign and magnitude of the E,., determines whether it is strong or weak. Solve: (a) Cl,(aq): strong oxidant (on the left, En = 1.359 V) (b) MnO, (aq, acidic): strong oxidant (on the left, E,.4 = 1.51 V) (©) Ba(s): strong reductant (on the right, E,_, = -2.90V) (4) _Zn(s): reductant (on the right, E,_., = -0.763 V) Hf the substance is on the left of a reduction half-reaction, it will be an oxidant; if it is on the right, it will be a reductant. The sign and magnitude of the E,_, determines whether it is, strong or weak. (2) _Na(s): strong reductant (on the right, E,_., = -2.71 V) 52320 Electrochemistry Solutions to Exercises 20.37 20.38 20.39 20.41 (bo) 0,(g): strong oxidant (on the left, Eig = 207V) (o) Ce*(aq): very weak reductant (on the right, Fag = 161V) (@) _Sn*(aq): reductant (on the right, E,., = 0.154 V) or weak oxidant (on the left, -0.136 V) Analyze/Pian. Follow the logic in Sample Exercise 20.8. Solve: (2) Arranged in order of increasing strength as oxidizing agents (and increasing reduction Potential): CuM(aq) < Ox(9) < Cr,0;* (aq) < Cl(g) < H,0,(aq) () Arranged in order of increasing strength as reducing agents (and decreasing reduction potential) H,0,(aq) < T-(aq) < Sn*(aq) < Zn(s) < Al(s) (2) _ The strongest oxidizing agent is the species most readily reduced, as evidenced by « large, positive reduction potential. That species is H,0,. The weakest oxidizing agent is the species that least readily accepts an electron. We expect that it will be very difficult to reduce Zn(s); indeed, Zn(s) acts as a comparatively strong reducing ‘agent. No potential is listed for reduction of Zn(s), but we can safely assume that it is less readily reduced than any of the other species present. (b) The strongest reducing agentis the species most easily oxidized (the largest negative ‘eduction potential). Zn, E,., = -0.76 V, is the strongest reducing agent and F-, E,.4 =2.87 V, is the weakest ‘Analyze/Plan. In order to reduce Eu to Eu”, we need an oxidizing agent, one of the reduced ‘Species from Table 20.1 or Appendix E. It must have a greater tendency to be oxidized than Eu has to be reduced. That is, E,., must be more negative than -0.43 V. Solve: ‘Any of the reduced species in Table 20.1 or Appendix E from a half-reaction with a reduction Potential more negative than -0.43 V will reduce Eu to Eu**. From the list of possible reductants in the Exercise, Al and H,C,O, will reduce Eu to Eu", ‘Any oxidized species from Table 20.1 or Appendix E with a reduction potential greater than 0.58 V will oxidize RuO,* to RuO,”. From the list of possible oxidants in the Exercise, Cr,0,* (aq) and CIO" (aq) will oxidize RuO,* to RuO,. Analyze/Plan. Follow the logic in Sample Exercises 20.9 and 20.10. Solve: (2) _ The more positive the emf of a reaction the more spontaneous the reaction. (b) Reactions (a), (b), (c) and (4) in Exercise 20.23 have positive E° values and are ‘spontaneous. 52420 Electrochemistry Solutions to Exercises 20.43 20.44 (0) AG" =-nFE*; F = 96,500 JWVemol e* = 96.5 kml e- 2023 (a) AG*= -2mole-x 2854 x 9.823 v= -158.839 = -159 kJ Vemole~ 20.23 (b) AG* = -2(96.5)(1.89) = -364.77 = -365 ks 2023 (ec) AG* = -2(06.5)(1.211 234k 20.23 (d) AG* = -6(96.5)(1.21) = -700.59 = -701 kd (a) AG =-nFE. The more positive the emf of a reaction, the more negative the value of, AG. ) (o) AG® = -nFE®; F = 96,500 J/Vemol. 96.5 kJ/V+mol e~ 20.24 (a) AG*= -2mole x 85) «2.87 v=.553.91 Vemole 20.24 (b) AG* = -2(96.5)(-3.24) =625.32 = 625 kd 20.24 (c) AG* = -2(96.5)(-1.21) = 233.53 = 234 kd 20.24 (d)_AG* = -2(96.5)(0.636) = -122.75 = -123 kJ Analyze/Plan. \n each reaction, Fe** -> Fe™ will be the oxidation half-reaction and one of the other given half-reactions will be the reduction half-reaction. Follow the logic in Sample Exercise 20.10 to calculate E* and AG* for each reaction. Solve: (a) 2Fe*(aq) + S,0,*(aq) + 4H’(aq) > 2Fe*(aq) + 2H,SO,(aq) E°=060V-0.77V=-0.17V ‘2Fe* (aq) + N,O(aq) + 2H"(aq) > 2Fe*(aq) + N.(9) + H,0(!) E°=-1.77V-0.77V=-254V Fe*(aq) + VO,"(aq) + 2H"(aq) > Fe™(aq) + VO™(aq) + H.0(1) E°=1.00V-0.77V=+0.23V (vb) | AG*=-nFE* For the first reaction, 96,500 J 1Vemol For the second reaction, AG” = -2(96,500)(-2.54) = 4.90 x 10? kJ AG* =-2 mol x x (-O.A7V)= 3.3 x10 Jor33 kd For the third reaction, AG* = -1(96,500)(0.23) = -22 kJ (@) 2F(aq) > 1s) +26" Ec = 0.536V Hg,*(aq) +2 e"-> 2Ha(l) Eg = 0.789V 2F (aq) + H9,"(aq) > 1s) + 2Ha(t) 0.789 - 0.536 = 0.253 V 96.5kJ Vemole AG AFE® = -2mole™x x 0.253 V=-48.8 kJ 52520 Electrochemistry Solutions to Exercises (b) ‘3{Cu'(aq) > Cu*(aq) + te] Eres =0.153V NO,"(aq) + 4H"(aq) + 3e- > NO(g) + H,O(1) Eg = 0.96 V 3Cu'(aq) + NO,"(aq) + 4H*(aq) > 3Cu*(aq) + NO(g) + 2H,0(!) E* = 0.96 -0.153=0.81V; AG* = -3(96.5)(0.81) = -2.3 x 107 kJ © 2{Cr(OH),(s) + SOH-(aq) > CrO (aq) + 4H,0() +3e] E,., =-0.13V [ClO-(aq) + H,0() + 2e° > C'(aq) + 204 (aq)] E.4= 0.89V 2Cr(OH),(s) + 3C1O"(aq) + 40H (aq) > 2Cr0,*(aq) + 3CI(aq) + SH_O(1) 0.89 - (-0.13) = 1.02 V; AG* = -6(96.5)(1.02) = -591 kJ & EMF and Concentration 20.45 20.46 20.47 20.48 (2) The Nemst equation is applicable when the components of an electrochemical cell are at nonstandard conditions. (>) Q= 1 ifall reactants and products are at standard conditions. (©) __ If concentration of reactants increases, Q decreases, and E increases. (2) No. As the spontaneous chemical reaction of the voltaic cell proceeds, the concentrations of products increase and the concentrations of reactants decrease, 0 standard conditions are not maintained. 8.314) Vemol x 298K x me ™ 96,5003 ‘The *2.303" is a factor to change natural logs into base-10 logs. The “0.0592 V" ‘assumes the cell operates at 298 K and that base-10 logs are used. (©) __ If concentration of products increases, Q increases, and E decreases. (>) 0.0582 = 2.303 a = 2.303 * Analyze/Plan. Given a circumstance, determine its effect on cell emf. Each circumstance changes the value of Q. An increase in Q reduces emf; a decrease in Q increases emf. Solve: tzn71P,, Z2n(s) + 2H'(aq) > Zn?*(aq) + H,(g), E=E*- = (HT 2059? tog a; a= (2) Py, increases, Q increases, E decreases (b) [Zn*"] increases, Q increases, E decreases (c) [H’] decreases, Q increases, E decreases (@ —_Noefect; does not appear in the Nemst equation Als) + 3Ag'(aq) > AP(aq) + 3Ag(s), = E* - 29592 ga; a= a oy 52620 Electrochemistry Solutions to Exercises 20.49 20.50 ‘Any change that causes the reaction to be less spontaneous (that causes Q to increase and ultimately shifts the equilibrium to the left) will result in a less positive value for E* (a) _ Increases E by decreasing [AI"] on the right side of the equation. (b) _Noeeffect; the “concentrations” of pure solids and liquids do not influence the value of K,, for a heterogeneous equilibrium. (©) _Noeffect; the concentration of Ag’ and the value of Q are unchanged. (4) Decreases E; forming AgCi(s) decreases the concentration of Ag’, which increases Q. Analyze/Pian. Follow the logic in Sample Exercise 20.11. Solve: (@) Ni*(aq) + 2e" > Nils) E..4= -028V Zn(s) > Zn™*(aq) + 26” Egg = -0.783V Ni*(aq) + Zn(s) > Ni(s)+Zn*(aq) —_E* = -0.28 - (-0.763) = 0.483 = 0.48 V 24 () B= Et- 2.0582 jog (20°) yan ne IN 0.483 2.0582 jo, (0.100) 0.0502 E = 0.483 - 9.0592 = 0.483 - 9.0592 tog (0.0333) 2? (09 6.00) 2 log (( ) E = 0.489 - 0.0592 C1.477) = 9.485 + 0.0437 = 0527 = 0.53 = 0.0592 |... (0.900) = E = 0.483 - 2.0592 jog (0-900) - 9.493 - 0.0193 = 0.464 = 0.46 V @ alr (0.200) m2 > Ce*(aq)) > Cr*(aq) + 3e" (a) 3[Ce"(aq) + 1 3Ce"(aq) + Cris) > 3Ce™(aq) + Cr*(aq) 393 1043 + _ 0.0582 jog [CoP IC], nag n [ce*"P 61 -(-0.74) = 2.35 V (b) E= £= 2.35 - 2.0582 jog (0.010)* (0.010) _ » 35 0.0592 log (1.250 « 10°) 3 (0p 3 €=2,25- 20582(8 909) 22.35 +0.176=253V (©) = 2.35 -9:0592 jog (0.85) (1.2) = 2 35 -0.0244=2.33V (0.35)° 52720 Electrochemistry Solutions to Exercises 20.51 20.52 20.53 20.54 Analyze/Plan. Follow the logic in Sample Exercise 20.11. Solve: (a) 4[Fe™(aq) > Fe™(aq) + te] E 0,(g) + 4H"(aq) + 4e" > 2H,0(1) E o771V 1.23V red 0 rea 4Fe*(aq) + 0,(g) + 4H"(aq) > 4Fe™(aq) + 2H,O(!) E°= 1.23 -0.771 = 0.459=0.46V (e) Exes 2.0592 jog [Fe > yg, ty = 1.00 102M n Fernie, 010) = 0.459 - 2.0592 (3.0)* (1.0 x 10°5}¢ (0.50) 4 = 0.459 V- 2.0592 jog log(246.9) E=0.459- see (2.303) = 0.459 - 0.0354 = 0.4236 = 0.42 V 2[Fe*(aq) + 1." > Fe*(aq)) Eng H,(g) > 2H*(aq) + 26" is 2Fe™(aq) + H,(g) > 2Fe*(aq) + 2H"(aq) LTT 000 V 771 0.000 = 0.771 (0) B= Be - 9.0892 jog (Fe T INT. tye som 4.0% 105, n=2 n [Fee PP, £ = 0.771 - 9.0522 jog (0.0010) (1.0 10 771 - 0.0582 Ing 9 x 19-7) 2 (1.50¥ (0.50) a B= 0,771 - 90502 (16.05) 20.71 +0.475 = 1246V Analyze/Pian. We are given a concentration cell with Zn electrodes. Use the definition of a concentration cell in Section 20.6 to answer the stated questions. Use Equation 20.16 to calculate the cell emf. For a concentration cell, Q = [dilutey/[concentrated]. Solve: (2) The compartment with the more dilute solution will be the anode. That is, the ‘compartment with [2n*] = 1.00 x 10° Mis the anode. (b) __ Since the oxidation half-reaction is the opposite of the reduction haif-reaction, E* is zero. (Exes. 25g aq; a= |2n™, ctte]/ [2n*, conc] 20 -2.0592 jog (1.00 « 10° E = 0 - 0.0582 jog (1.00 x 10) - go799y 2 8 E00) (@) Inthe anode compartment, Zn(s) -> Zn**(aq), 80 [Zn**] increases from 1.00 x 10° M. In the cathode compartment, Zn**(aq) > Zn(s), 80 [Zn] decreases from 5.00 M. (2) The compartment with 0.0150 M Cr (aq) is the cathode. () E*=0v 52820 Electrochemistry Solutions to Exercises () E=E*- 2.059 9g Q; Q=[CF, dilute] /[Cr, cone.) 0.0592 oe (0.0150) _ =0- k 0.132 09 "255) (@) Inthe anode compartment, [Cr] will decrease from 2.55 M. In the cathode, [Cr will increase from 0.0150 M. 20.55 20.56 20.87 20.58 Analyze/Plan. Follow the logic in Sample Exercise 20.12. Solve: oper + 0.0582 gg Pu t20"1 a or ; E* = 0.0 V-(-0.763 V) = 0.763 V 0.684 = 0.763 - 2: 82 » (og(P,, Zn] ~2 log Hp = 0.763 - 20582 « .0.5686-2 0g 1H") 0.684 -0.0168 -0.763 0.684 = 0.763 + 0.0168 + 0.0592 log [H"; = Jog [H'T; log [H"] 0.0592 log [}H"] = -1.6188 = [H'1= 0.0241 = 0.02 M; pH=1.6 (a) E*=-0.136V- (-0.126 V) =-0.010V; n=2 nee 2 0.22 =-0.010 - 2.9582 jpg IPO") = .910- Soe fog [Pb*] 2 sn? 7.00 = 20.2302). 7 a17% x log [Pb] = SSE) = 7.770 = 7.8; [PbM]= 1.7 « 10%=2* 109M (0) For PPSO,(S), Ky, = [Pb™] [S07] = (1.0)(1.7 * 10°) = 1.7 x 10° 0.0592 V n Analyze/Plan. Follow the logic in Sample Exercise 20.14. E' =e (00 Ke" Tosoav ° log Keg (@ 28 - (-0.440) = 0.16 V, n= 2 (NP* +2e" > Ni) 2(0.16) = = 2.54% 10°=3% log Kya = SET) = 5.4054 = 5.4; K,,= 2.54. 10° = 3 x 105 (0) E°=0-(-0.277)= 0.27 V; n=2(2H" +26 > H,) = 20.277) - 9 959 = =23% log Ka = “Fogg = 9-958 = 9.36; K,=2.3 10° © 51 - 1.065 = 0.445 = 0.45 V; n= 10 (2MnO,-+ 10e" -> 2Mn*?) = 100.445) . = 1.5% 107 = 107 log Ky, = TAOS) = 75.169 = 75; Ky= 1.5% 107 = 10 — a Jog Ky; log Ka = 0. or] 52920 Electrochemistry Solutions to Exercises (a) 1.00 V - (-0.799 V) = 0.201 = 0.20V; n=2 (Ni? +20" > Ni) log k= 20:201Y) = 6 7005 = 0.0592V K,, = 6.17 x 10° = 6 x 10° (b) 1.61 V-0.32 V=1.29V; n=3(3Ce"+3e > 3Ce™) = 3(1.29) . = 65.4; K,=2.35 x 10% =2 109 Kua = J gggp = 85372 = 65.4; K,,= 2.35 x 10% = 2 x 10% (©) E° = 0.36 V- (-0.23 V) = 0.59, n=4 (4Fe(CN),* + 4e” > 4Fe(CN),*) log K,,= 40-59) = 39.865 = 40; K.,=7 x 10% = 10° 0.0592 20.59 Anayeartn _Fotlw he oi in Sample Eerie 20.14 Ere 0582V tog k,: Ka WooKa" asaay* Same (2) log k= VO177V) = 2 9999 =2.99; K,= 9.8 x 107 0.0592 V (b) log k,,= 20-177) = 5 9707 = 5.98; K,= 9.5 x 10° = 3OAT7V) ~ 9 9696 = 8.97; K.= x 10°=9.3 «1 (© waKe= Sossry ane 2060 + = 20582V tog ks <= ogee log Ke, 0.0592v = DOSE2V tog 5.5 x 10%, n=2 oarv 8 . Batteries; Corrosion 20.81 (a) —Abatteryis aportable, self-contained electrochemical power source composed of one or more voltaic cells. (0) Aprimary battery is not rechargeable, while a secondary battery can be recharged. (©) _No. No single voltaic cell is capable of producing 7.5 V. If a single voltaic cell could be designed to produce 2.5 V, three of these cells connected in series would produce the desired voltage. 2062 (a) The emf of a battery decreases as it is used. This happens because the concentrations of products increase and the concentrations of reactants decrease. According to the Nernst equation, these changes increase Q and decrease E,,». (b) The major difference between AA- and D-size batteries is the amount of reactants Present. The additional reactants in a D-size battery enable it to provide power for a longer time. 53020 Electrochemistry Solutions to Exercises 20.63 20.64 20.65 20.66 20.67 Analyze/Pian. Given mass of a reactant (Pb), calculate mass of product (PbO,). This is a stoichiometry problem; we need the balanced equation for the chemical reaction that occurs in the lead-acid battery. Then, g Pb -> mol Pb -> mol PbO, > g PbO,. Solve: The overall cell reaction (Equation [20.19)) is: Pb(s) + PbO,(s) + 2H"(aq) + 2HSO, (aq) > 2PbSO,(s) + 2H,0(!) AmolPb , 1MOlPbO, | 239.29Pb0, 382 g Pb es 2 2072gPb tmolPb — tmol PbO, = 441g PbO, ‘The overall cell reaction is: 2MnO,(s) + Zn(s) + 2H,O(I) > 2MnO(OH)(s) + Zn(OH),(s) 1imolZn_, 2molMnO, | 86.94gMnO, 12.9g2nx_tmalzn_ , 2mMOAMNO, , 06.94gMnO, 920*55399zn ~ molZn ~ tmolMnO, = 34.3 g MnO, reduced Analyze/Plan. We are given a redox reaction and asked to write half-reactions, calculate E*, ‘and indicate whether Li(s) is the anode or cathode. Determine which reactant is oxidized and which is reduced. Separate into half-reactions, find E,_,., for the half-reactions from Appendix E.and calculate E*. Solve: (2) Li(s) is oxidized at the anode. ) Ag,Cr0,(s) + 26° > 2Ag(s) + CrO*(aq) E oy = 0.446V 2ILi(s) > Li"(aq) + 167] E,.4 = -3.05V Ag,Cr0,{(s) + 2Li(s) > 2Ag(s) + CrO,-(aq) + 2Li"(aq) * = 0.448 V - (-3.05 V) = 3.496 = 3.50V (©) The emf of the battery, 3.5 V, is exactly the cell potential calculated in part (b). (@) — HgO(s) + Zn(s) > Hg(!) + Zn0(s) () Eo) = Egg (Cathode) - E,”. (anode); E,., (anode) = E,.,-E,., = 0.098 - 1.35 =-1.25V (©) —_E,., is different from Zn*(aq) +2e” > Zn(s) (-0.76 V) because in the battery the ced process happens in the presence of base and Zn is stabilized as ZnO(s). Stabilization of the product of a reaction increases the driving force for the reaction, 80 E* is more positive. Analyze/Plan. (a) Consider the function of Zn in an alkaline battery. What effect would it have ‘on the redox reaction and cell emf if Cd replaces Zn? (b) Both batteries contain Ni. What is the difference in environmental impact between Cd and the metal hydride? Solve: 531