This document discusses solutions to questions about potentiometry. It covers topics like standard reduction potentials, Nernst equation calculations, and junction potentials. Sample questions are provided about oxidation-reduction reactions, concentration cells, and reference electrodes used in potentiometric titrations.
This document discusses solutions to questions about potentiometry. It covers topics like standard reduction potentials, Nernst equation calculations, and junction potentials. Sample questions are provided about oxidation-reduction reactions, concentration cells, and reference electrodes used in potentiometric titrations.
This document discusses solutions to questions about potentiometry. It covers topics like standard reduction potentials, Nernst equation calculations, and junction potentials. Sample questions are provided about oxidation-reduction reactions, concentration cells, and reference electrodes used in potentiometric titrations.
This document discusses solutions to questions about potentiometry. It covers topics like standard reduction potentials, Nernst equation calculations, and junction potentials. Sample questions are provided about oxidation-reduction reactions, concentration cells, and reference electrodes used in potentiometric titrations.
1. a) NO3-(aq) + Cu(s) X NO2(g) + Cu2+(aq) (acidic soln)
+5 0 +4 +2
Cu is being oxidized and N is being reduced.
oxidation: ( Cu X Cu2+ + 2e- )
reduction: ( NO3- + e- + 2H+ X NO2 + H2O ) x 2
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Cu + 2NO3- + 2e- + 4H+ X Cu2+ + 2e- + 2NO2 + 2H2O
b) MnO4-(aq) + Br-(aq) X MnO2(s) + BrO3-(aq) (basic soln)
+7 -1 +4 +5
Br is being oxidized and Mn is being reduced.
oxidation: ( Br- + 6OH- X BrO3- + 6e- + 3H2O )
reduction: ( MnO4- + 3e- + 2H2O X MnO2 + 4OH- ) x 2
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2 - - - Br + 6OH + 2MnO4 + 6e + 4H2O - X BrO3 - + 6e + 3H2O + 2MnO2 + 8OH- -
Br- + 2MnO4- + H2O X BrO3- + 2MnO2 + 2OH-
Solutions for Potentiometry Questions
Check for Understanding 11.3
1. The posted table of values are standard potentials for reduction half reactions. The value for the standard oxidation half-cell potential E0Ag/AgCl is numerically equal to E0AgCl/Ag with a change of mathematical sign. Thus, E0Ag/AgCl = -(0.222 V) = -0.222 V.
Check for Understanding 11.4
1.
For μ = 0.10 M, γFe2+ = 0.405 and γFe3+ = 0.18. Thus,
Check for Understanding 11.5
1.
Reference Electrode Titration Solution
Ag(s) AgCl(s) KCl(sat’d) Cl-(aq) AgCl(s) Ag(s)
2. The anode half reaction is:
anode: Ag(s) + Cl-(aq) º AgCl(s) + e-
The reduction reaction at the cathode is the reverse of the anode reaction.
cathode: AgCl(s) + e- º Ag(s) + Cl-(aq)
Solutions for Potentiometry Questions
3. For the anode half cell, the Nernst equation is:
The Nernst equation for the cathode is:
The overall cell potential (Ecell) is the sum of the half-cell potentials. For this potentiometric chloride titration cell,
Check for Understanding 11.6
1. In 0.100 M KCl, [Cl-] = 0.100 M and μ = 0.10 M. Thus, γCl- = 0.755 and aCl- = [Cl-]γCl- = (0.100)(0.755) = 0.0755.
2. For a KCl-saturated Ag/AgCl reference electrode, Eref ~-0.197 V, and
aCl- = 0.0755 in a 0.100 M KCl solution. Substituting these values gives Ecell ~ 0.091 V.
3. At the equivalence point, aCl- ~ aAg+ and Ksp = aAg+aCl- ~ aCl-2. Thus, aCl- = (Ksp)½ = (1.8 x 10-10)½ = 1.34 x 10-5.
Check for Understanding 11.7
1. a) There is a net migration of H+ and Cl- to the solution of lower
concentration. Since H+ has a higher mobility than Cl-, the solution of lower concentration is at the more positive potential.
b) There is a net migration of K+ and Cl- to the solution of lower
concentration. Since Cl- has a higher mobility than K+, the solution of higher concentration is at the more positive potential. Solutions for Potentiometry Questions
2. Since the mobilities of K+ and NO3- are closer than the mobilities of K+ and Cl-, there is less separation of charges as a result of ion migration from high concentration to low concentration. This reduces the junction potential of a KNO3 solution interface compared with that for a KCl solution interface. Since K+ has a higher mobility than NO3- but lower than that for Cl-, the sign of the junction potential for KNO3 will be the reverse of that for KCl.
