19 Applications of Standard Electrode Potentials
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1 9 Applicatins f Standard lectrde Ptentials ( Calculating thermdynamic cell ptentials ( Calculating equilibrium cnstants fr redx reactins ( Cnstructing redx titratin curves 9A Calculating Ptentials f lectrchemical Cells cell right left x. 9- Calculate the thermdynamic ptential f the fllwing cell and the free energy change assciated with the cell reactin. Cu Cu + (. M Ag + (. M Ag Ag + + e - Ag(s º.799 V Cu + + e - Cu(s º.7 V lg. Ag + /Ag.59.7 lg. Cu + /Cu V.867V cell Ag + - Cu V ΔG fr Cu(s + Ag + Cu + + Ag(s ΔG -nf cell C.4 V -795J (8.99 Kcal x. 9- Calculate the thermdynamic ptential f the cell Ag Ag + (. M Cu + (. M Cu cell Cu + - Ag V x. 9- Calculate the ptential f the fllwing cell and indicate whether it is galvanic r electrlytic (see Fig. 9-. Pt UO + (.5 M,U (. M, H + (. M Fe + (. M, Fe (.5 M, Pt Fe + e - Fe + º.77 V + UO + 4H + + e - U + H O º.4 V [Fe lg [Fe + cathde ( V.59 [U.4 lg + [UO [H.4 - (.6.4 V..59 lg lg.5. ande + 4 4
2 cell cathde ande V ( psitive sign galvanic Fig. 9- Cell fr ex. 9- Fig. 9- Cell withut liquid junctin fr ex. 9-4 x. 9-4 Calculate the theretic ptential fr Ag AgCl(sat'd, (. M H (.8 atm, Pt H + + e - H (g º. V AgCl(s + e - Ag(s +Cl - º. V.59.8 cathde. lg.977v. ande..59 lg..6 V cell V The negative sign means that the cell reactin H + + Ag(s + Cl - H (g + AgCl(s is nnspntaneus, and thus the cell is electrlytic. x. 9-5 Calculate the ptential fr the fllwing cell using (a cncentratin and (b activities: Zn ZnSO 4 (x M, PbSO 4 (sat d Pb, where x 5. -4,. -,. - and 5. -, (a In a neutral slutin, [SO - 4 c ZnSO 4 x 5. -4, PbSO 4 + e - - Pb(s + SO 4 º -.5 V Zn + + e - Zn(s º -.76 V 8
3 PbSO /Pb.59.5 lg(5. 4.5V lg.86v Zn + /Zn 4 5. cell right left -5 ( V (b Calculate activity cefficient fr Zn + and SO 4 - μ 4 4 ( lgγ 8.6, γ -.8, γ 4 SO4 Zn PbSO 4 /Pb SO.59.5 lg( V lg.86v Zn + /Zn cell right left -5 ( V Table 9- ffect f Inic Strength n the Ptential f a Galvanic Cell [ZnSO 4, M μ, Inic Strength, V, based n Cncentratin, V, based n Activity.85, V, xperimental Values x. 9-6 Calculate the ptential required t initiate depsitin f Cu frm a slutin that is. M in CuSO 4 and cntains sufficient H SO 4 t give a ph f 4.. O (g + 4H + + 4e - H O º +.9 V Cu + + e - Cu(s º +.7 V.59.7 lg.78v Cu /Cu lg 4 [H.59.9 lg 4 atm O /H O po 4 + cell right left V.99V The cell reactin Cu + + H O O (g + 4H + + Cu(s is nnspntaneus and that t cause Cu t be depsited, we must apply a cathde ptential mre negative than -.74 V 9
4 9B Determining Standard Ptentials xperimentally x. 9-7 Pt,H (. atm (.5 - M, AgCl(sat d Ag º +.55 V Calculate the º fr the half-reactin AgCl(s + e - Ag(s +Cl - right AgCl - c Cl H + + e - ½ H (g cell right left [ cell AgCl AgCl AgCl.59 lg( γ.59 lg( γ.55 AgCl Cl Cl.59 lg( γ ( ( γ ( γ left (γ.59 lg H /H ph.59 lg (γ ( c + H + p H +.59 lg H /H (γ + ( c H (γ + ( c H..59 lg p H + ( γ Cl ph ( c (.945(.99( lg. 9C Calculating Redx quilibrium Cnstants Cu(s + Ag + Cu + + Ag(s Cu Cu + (x M Ag + (y M Ag at chemical equilibrium r x x x x4 + [Cu Keq + [Ag cell right left Ag Cu right left Ag Cu Ag lg Cu lg + + [Ag [Cu Ag + + e - Ag(s º.799V Ag.59 eq H.. V + Cu lg lg lg lg K [Ag.59 [Cu.59 [Cu [Ag
5 ( Ag.59 Cu [Cu lg [Ag + + lg K eq lgk eq ( B n.59 A ln K eq ΔG RT nf RT cell at 5 C lg K eq ncell.59 n ( right.59 left x. 9-8 Calculate the K eq fr the reactin Cu(s + Ag + + [Cu ( lg Keq lg [Ag.59 K eq antilg Cu + + Ag(s x. 9-9 Calculate the K eq fr the reactin Fe + I - Fe + + I - Fe + e - Fe +.77 V I - + e - I -.56 V + + Fe /Fe Fe /Fe +.59 [Fe lg [Fe -.59 [I lg I/I I/I - [I at equilibrium Fe /Fe I/I +.59 [Fe - + lg.59 [I lg Fe /Fe - - [Fe I/I - [I ( Fe /Fe I [Fe [I [Fe [I lg lg lg [Fe [I [Fe [I lg K eq + - ( [Fe [I + Fe /Fe I lg - [Fe [I.59 ( Fe /Fe I / I ( K eq antilg / I -
6 x. 9- Calculate the K eq fr the reactin MnO Mn + + H O 5MnO (s + 4H + MnO H + + 6e - MnO (s + 4H O º.695 V MnO (s + H + + 6e - Mn + + 6H O º. V MnO 4 - /MnO MnO /Mn [Mn lg. lg lg [MnO 4 [H 6 + [H 6( lg.59 [MnO [H + 4 [H lg K eq lg [MnO 4 [Mn K eq antilg lg lg [H [Mn [MnO 4 [Mn [H 9D Cnstructing Redx Titratin Curves 9D- lectrde Ptentials during Redx Titratins Fe + + Ce Fe + Ce Ce /Ce Fe /Fe + system In SH Ce, Ce, Fe, Fe + Pt Mst end pint in xidatin/reductin titratins are based n the rapid changes in system that ccur at r near chemical equivalence. Befre the equivalence pint, system calculatins are easiest t make using the ernst equatin fr the analyte. Beynd the equivalence pint, the ernst equatin fr the titrant is mre cnvenient. quivalence-pint Ptentials at the equivalence pint [Ce eq.59 lg and eq Ce Fe [Ce + [H + [Fe.59 lg [Fe + [Ce [Fe eq +.59 lg + Ce Fe [Ce [Fe Ce Fe ([Fe [Ce, [Fe + [Ce Ce eq + Fe
7 x. 9- Obtain an expressin fr the equivalence-pint ptential in the titratin f.5 M U with. M Ce. Assume bth slutins are. M in H SO 4. U + Ce + + H O UO + Ce + 4H + UO + + 4H + + e - U + H O º.4 V Ce + e - Ce (frmal ptential º'.44 V.59 [U eq + lg (a UO [UO [H '.59 [Ce eq lg (b Ce [Ce a + b ' [U [Ce eq lg UO Ce [UO [Ce [H at equivalence [U [Ce / and [UO + [Ce / ' + + UO Ce.59 [Ce [Ce eq lg + 4 [Ce [Ce [H ' + + UO Ce 9D- The Titratin Curves.59 lg + 4 [H ph dependent Titratin f 5. ml f.5 M Fe + with. M Ce in a medium that is. M in H SO 4 at all times. Ce + Fe + Fe + Ce Ce + e - Ce º'.44 V (M H SO 4 Fe + e - Fe + º'.68 V (M H SO 4 Initial Ptential Ptential After the Additin f 5. ml f Cerium(IV [Fe [Ce [Ce [Fe + [Ce + [Ce [Fe.5/55. and [Fe +./ / 55. system +.68 lg.64 V.5 / 55.
8 quilvalence-pint Ptential ' ' Ce Fe + eq.6 V Ptential After the Additin f 5. ml f Cerium(IV [Ce [Fe [Ce + [Fe [Ce.59.5 / lg.44 lg. V [Ce. / 75. Table 9- lectrde Ptential versus SH in Titratins with. M Ce Ptential, vs, SH Reagent Vlume, ml 5. ml f.5 M Fe + 5. ml f.5 M U quivalence Pint Oxidatin/reductin curves are independent f the cncentratin f the reactants except when the slutin is very dilute. Fig. 9- Titratin curves fr.m Ce titratin. A: Titratin f 5. ml f.5 M Fe +. B: Titratin f 5. ml f.5 M U. 4
9 9D- ffect f Variables n Redx Titratin Curves Reactant cncentratin titratin curves are usually independent f analyte and reagent cnc. Cmpleteness f the Reactin cmpleteness f the reactin change in system in the equivalence-pint regin Fig. 9-5 ffect f titrant electrde ptential n reactin cmpleteness. The standard electrde ptential fr the analyte ( A is.v; starting with curve A, standard electrde ptentials fr the titrant ( T are.,.,.8,.6 and.4, respectively. Bth analyte and titrant underg a ne-electrn change. 9 Oxidatin/Reductin Indicatrs *Specific Indicatrs: react with ne f the participants in the titratin t prduce a clr. starch: frm a deep blue cmplex with idine KSC: frm a red Fe(III/thicyanate cmplex with Fe(III *General Redx Indicatrs: respnd t the ptential f the system. In x + ne - In.59 [In red lg red Inx/Inred n [Inx a clr change In x In red [Inred [Inx [In red [Inx.59 In ± n Fr a typical indicatr t underg a useful transitin in clr, the titrant must cause a change f.8/n V in the ptential f the system. Fr many indicatrs, n is, s a change f.59 V is sufficient. Irn(II Cmplexes f Orthphenanthrlines (phen Fe + e - (phen Fe + pale blue red 5
10 Table 9- Selected Oxidatin/Reductin Indicatrs Indicatr Clr Transitin Oxidized Reduced Ptential, V Cnditins 5-itr-,- phenanthrline irn(ii cmplex Pale blue Red-vilet +.5 M H SO 4, -Diphenylamine dicarbxylic acid,-phenanthrline irn(ii cmplex 5-Methyl-,- phenanthrline irn(ii cmplex Blue-vilet Clrless M H SO 4 Pale blue Red +. M H SO 4 Pale blue Red +. M H SO 4 riglaucin A Blue-red Yellw-green M H SO 4 Diphenylamine Red-vilet Clrless +.85 Dilute acid sulfnic acid Diphenylamine Vilet Clrless +.76 Dilute acid p-thxychrysidine Yellw Red +.76 Dilute acid Methylene blue Blue Clrless +.5 M acid Indig tetrasulfnate Blue Clrless +.6 M acid Phensafranine Red Clrless +.8 M acid Fe +,-phenanthrline ferrin (phen Fe + O H C 5-nitr-,- phenanthrline 5-methyl-,- phenanthrline 6
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