47O CHAPTERlB lntroduction to Electrochemistry

QUESTIONS A}.ID PROBLEMS

*18-8. Identifr the oxidizing agent and the reducing agent
N0TE, Numerical data are molar analytical c0ncentrations where the full
formula of a species is provided. Molar equilibrium concentrations are on the left side of each equation in Problem 18-7;
supplied for species displayed as ions. write a balanced equation for each half-reaction.
18-1. Briefly describe or define l8-9. Write balanced net ionic equations for the following
*(a) oxidation. reactions. Suppiy H+ and/or H2O as needed to ob-
(b) reducing agent. tain balance.
*(c) *(a) MnOa- + VO2+ --+ Mn2+ + V(OH)4+
salt bridge.
(d) liquid junction' (b) I, + HrS(g) --> I-+SG)
*(e) Nernst equation. *(c) Cr2O72 + U4* -+ Cr3+ + UO22*
I ti-2. Briefly describe or define (d) Cl + MnO2(s) -t Clrk) + Mn2+
*(a) electrode potential. *(e) IO3 + I -+ Ir(aq)
(b) formal potential' (f) Iot + I- + cl + ICl2
*(c) standard electrode potential. *(g) HPo32-+ Mnoa- + oH -+ Pol + MnOl
(d) liquid-junction Potential. d-,) scN- + Bro3 -+ Br- + SO42- + HCN
(e) oxidation potential.
*(i) vrn + v(oH)4+ -+ vo2+
18-3. Make distinction benveen
a clear (j) Mnoa- * Mn2+ + oH + Mno2(s)
*(a) oxidation and oxidizing agent. 1B-10. Identifr the oxidizing agent and the reducing agent
(b) an electrolytic cell and a galvanic cell' on the left side ofeach equation in Problem 18-9;
*(c) the cathode of an electrochemical cell and the write a balanced equation for each half-reaction.
right-hand electrode. '18-1 I . Consider the following oxidation/reduction reactions:
(d) a reversible electrochemical cell and an irrevers- AgBr(i) + V2+ -+Ag(s) + V3+ + Br
ible electrochemical cell.
*(e) the standard electrode Potential and formal + 2Fe(CN)l _+ Tl+ * 2Fe(CN)r3-
Tl3+
Potential. 2Y3* + zn(l --> 2Y2* + zn2+
* 8-4. The following entries are found in a table of standard
Fe(CN)e3 + Ag(s) + Br --+ Fe(CN)l- * AgBr(s)
1

electrode potentials:
-t 2e : Sror'- a 1l+ + 2SOa2 + Tl3+
Ir(s) 2I- Eo 0.5355Y
= (a) \Write each net process in terms of two balanced
I2@Q + 2e- Eo :0.615Y
=21 half-reactions.
'What is the significance of the difference between (b) Express each hallreaction as a reduction.
these two standard Potentials? (c) Arrange the half-reactions in (b) in order of
-18-5. Why is it necessary to bubble hydrogen through the
decreasing effectiveness as electron acceptors'
electrolyte in a hydrogen electrode? 18-12. Consider the following oxidation/reducdon reactions:
l8-6. The standard electrode potential for the reduction
2H+ + Sn(s) * Sn2+
-+ H2(g)
of Ni2+ to Ni is -0.25Y. Would the potential of a
nickel eiectrode immersed in a 1.00 M NaOH solu- Ag* * Fe2* --) Ag(s) * Fe3+
tion saturated with Ni(OH)2 be more negative than
Sn4* + Hr(g) --> Sn2* + 2H*
E$r ,*, or less? ExPlain.
18-7. lVrite balanced net ionic equations for the following 2Fe3+ + Sn2* --+ 2Fe2+ + sn4+
reactions. Supply H+ and/or H2O as needed to ob-
tain balance. Sn2* + Co(s)+Sn(i) + Co2+
*(a) Fe3+ -l Sn2+ -> Fe2+ * Sna+ (a) \Write each net process in terms of two balanced
(b) Cr(s)+Ag+ -+ Cr3+ + AgG) half-reactions.
*(c) NO3 + Cu(s) + NO2Q) * Cu2* (b) Express each half-reaction as a reduction.
(d) MnOa- + H2SO3 --+ Mn2+ + SO42- (c) Arrange the half-reactions in (b) in order of de-
*(e) Ti3* + Fe(CN)63- --+ TiO2+ * Fe(CN)na-
creasing effectiveness as electron accePtors.
(f) H2O, I Cea+ --+ Ozk) * Ce3* .l 8-13. Calcuiate the potential of a copper electrode immersed in
-(g) ASG) + I- + Sn4* -+Agl(s) * Sn2+
(a) 0.0380 M Cu(NO)r.
thl uor2* -l Zn(s) --) U4* * zn2+ (b) 0.0650 M in NaCl and saturated with CuCl.
*(i) HNO, * MnOa- -+ NOf * Mn2+ (c) 0.0350 M in NaOH and saturated with Cu(OH):.
(,) HNTNNH2 + IO3- + Cl -+ Nzk) + ICl2 (d) 0.0375 M in Cu(NHr)|+ and 0.108 M in
NHr (Fa for Cu(NH3)a2* it 5.62 x 1011).
 Questions and Problems 477

(e) a solution in which the molar analytical concen- l8-19. The following half-cells are on the left and coupled
tration of Cu(NO3)2 is 3.90 x 10 3 M, that for with the standard hydrogen electrode on the right to
HrY is 3.90 X 1o-2 M g: EDTA), and the form a galvanic cell. Calculate the cell potential. In-
pH is ffxed ar.4.00. dicate which electrode would be the cathode if each
Calculate the potential of azinc electrode immersed in cell were short circuited.
(a) 0.0500 M Zn(NO)r. (a) CulCu2+(0.0805 M)
(b) 0.0200 M in NaOH and saturated with Zn(OH)u. (b) CulCuIGatd), KI(0.0993 M)
(c) 0.0150 M in Zn(NH)a2+ and 0.350 M in (c) Pt, Hr(0.914 atm)lHCl(1.00 x 10-1M)
NHr-Fn for Zn(NH3)a'* it7.76 x 708. (d) ptlFe3+(0.0886 M), Fe2*(0.1420 M)
(d) a solution in which the molar analytical concen- (e) AglAg(CN)2- Q.0778 M), KCN(0.0651M)
tration of Zn(NO3)2 is 4.00 X 10-3, that for -18-20. The solubiliry-product constant for Ag2SO3 is 1.5 x
HrY2- is 0.0550 M, and the pH is fixed at 9.00. 10 14. Calculate Eo for the process
Use activities to calculate the electrode potential of a
Ag2SO3(s) * 2e- j 2Ag-l SO32-
hydrogen electrode in which the electrolyte is 0.0100
M HCI and the activicy of H2 is 1.00 atm. l8-21. The solubility-product constant for Ni2P2O7 is 1.7
Calculate the potential of a piatinum electrode im- x 10-13. Calculate E0 for the process
mersed in a solurion that is
(a) 0.0160 M in KrPtCla and0.2450 M in KCl.
Ni2P2O7(s) * 4e- i 2NiG) + PrO-*-
(b) 0.0650 M in Sn(SOa)rand3.5 x 10-3 M in "18-22. The solubility-product constant for TlrS is 6 X
SnSOa. 10-22. Calculate E0 for the reaction
(c) buffered to a pH of 6.50 and saturated with
TlzS(s)+2e
H2Q) at 1.00 atm. =2TlG)+S'7
(d) 0.0255 M in VOSOa, 0.0686 M in V2(SOa)3, 18-23. The solubility product for Pb3(AsO)2is 4.1 X
and 0.100 M in HClOa. 10-36. Calculate E0 for the reaction
(e) prepared by mixing 25.00 mL of 0.0918 M
Pbr(l'so4)rfu) * 6e- j 3PbG) + 2AsOaz-
SnCl2 with an equal volume of 0.1568 M FeClr.
(f) prepared by mixing 25.00 mL of 0.0832 M *18-24. Compute Eo for the process
V(OH)4+ with 50.00 mL of 0.01087 M ZnY2 * 2e- i Zn(s) *Ya
Vr(SO4)3 and has a pH of 1.00.
Calculate the potential of a platinum electrode im- whereY4 is the completely deprotonated anion of
mersed in a solution that is EDTA. The formation constant for ZnY2- is 3.2 x
(a) 0.0613 M in KaFe(CN)6 and 0.00669 M in 1016.
-18-25. Given the formation constants
QFe(CN)6.
(b) 0.0400 M in FeSOa and 0.00915 M in , rr.1.
n l+ -i
-le- r i FeY Kr: 1.3 X 1025
Fe2(SOa)3.
Fe2* + ya- FeY2- Kr:2.1 x 1014
(c) buffered to a pH of 5.55 and saturated with H2 =
at 1.00 atm. calculate C for the process
(d) 0.1015 M in v(oH)4+,0.0799 M in VO2+,
FeY-*e
and 0.0800 M in HClOa. =FeY2-
(e) prepared by mixing 50.00 mL of 0.0607 M l8-25. Calculate E0 for the process
Ce(SO+)z with an equal volume of 0.100 M + 2NH3
Cu(NH3)a2* i e- i Cu(NH3)r+
FeCl2 (assume solutions were 1.00 M in H2SOa
and use formal potentials). given that
(f) prepared by mixing 25.00 mL of 0.0832
M Vr(SO4)3 with 50.00 mL of 0.00628 M
cu+ + 2NH3
= Cu(NH3)z* Fz: 7.2 x 1o1o
V(OH)4+ and has a pH of 1.00.
Cu2n + 4NH,
= cu(NH3)a2* Fq: 5.62 x 101i
If the following half-cells are the right-hand elec- 7. For a PtlFe3+, Fe2* half-cell, find the potential for
trode in a galvanic cell with a standard hydrogen the following rarios of [Fe3+]/[Fe2+]: 0.001, 0.0025,
electrode on the left, calcuiate the cell potential. If 0.005, 0.0075, 0.010, 0.025, 0.050, 0.075, 0.100,
the cell were shorted, indicate whether the electrodes 0.250, 0.500, 0.750, 1.00, 1.250, t.50, t.75,2.50,
shown would act as an anode or a cathode. 5.00, 10.00, 25.00,75.00, and 100.00.
(a) Ni lNi2+(0.0883 M) 1B-28. For a PtlCea*, Ce3* half-cell, find the potential for
(b) AglAgl(satd), KI(0.0898 M) F=t
ri rll the same ratios of [Ce4*]/[Ce3n] as given in Problem
(c) Ptl02(780 rorr). HCI(2.50 x l0 4 M) 18-27 for [Fe3*]/[Fe2*].
(d) ltlsn2*10.0893 M), sn4+(0.215 M) tr 8-29. Plot the half-cell potential versus concentration ratio
(e) AglAg(sro3)23 (0.00891 M), Na2S2o3(0.1035 M) for the half-cells of Problems 18-27 and 18-28. How
472 CHAPTERlB lntroduction to Electrochemistry
would the plot look if potential were plotted against
log(concentration ratio) ? would expect the cell to provide accurate mea-
18-30. Challenge Problem: At one time, the standard hy-
drogen electrode was used for measuring pH.
(a) Sketch a diagram ofan electrochemical cell that
could be used to measure pH and label all parts
of the diagram. Use the SHE for both half-cells.
(b) Derive an equation that gives the potential of
the cell in terms of the hydronium ion concen-
trarion [H:O*] in both half-cells.
(c) One half-cell should contain a solution of known
hydronium ion concentration, and the other
should contain the unknown solution. Solve the
equation in (b) for the pH of the solution in the
unknown half-cell.
(d) Modify your resulting equation to account for
activity coefficients and express the result in
terms of pas - -1og aH, the negative logarithm
oFrhe hydronium ion acriviry.
pH slide rule
Explain the principles of operation of this slide rule and
describe how it works. '*{hat reading would you obtain
from the slide rule for a hydronium ion concentration
5P E. Klopsteg, Ind. Eng. Chem,1922, I4(5),399, DOI:10.1021/ie50149a011
(e) Describe the circumstances under which you
surements of pas.
(f) Could your cell be used to make practical abso-
lute measurements of pa11 or would you have to
calibrate your cell with solutions of known pag?
Explain your answer in detail.
(g) How (or where) could you obtain solutions of
known pa11?
(h) Discuss the practical problems that you might
encounter in using your cell for making pH
measurements.
(i) Klopsteg5 discusses how to make hydrogen elec-
trode measurements. In Figure 2 of his paper, he
suggests using a slide rule, a segment of which is
shown here, to convert hydronium ion concen-
trations to pH and vice versa.
4
of 3.56 X 10 M? How many significant figures are
there in the resulting pH? \7hat is the hydronium ion
concentration ofa solution ofpH : 9.85?
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