EMA 4324 Problem Set 3b KEY

2-7. [Note that I have modified the problem in the textbook.] A

specimen of iron [Fe] is placed in an air-saturated NaCl solution of
unknown concentration. Solution pH is determined to be 1.0.
Connecting the iron electrode to the negative terminal of a high
impedance voltmeter, a cell voltage of +0.50 volts is measured
against a copper/saturated copper sulfate reference electrode.
Considering the chemical composition of the system, what anodic
and cathodic reactions are possible?

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V = E(ref) - E(Fe+2/Fe); E(Fe+2/Fe) = E(ref) - V = 0.318 - 0.50 =
-0.182v. This potential is a measured electrode potential which
results from the reactions taking place on the surface of the
electrode, as distinguished from a reaction potential which is
determined by the thermodynamics for a particular process or
reaction [free energy stuff].

so... processes with potentials more positive than -0.182v will

proceed as reductions, processes with potentials more negative than
-0.182v will proceed as oxidations - these potentials are the Nernst
potentials for the various processes.

Fe+2 +2e- = Fe; for Fe+2 =10-6 M, Eo = -0.441, E = -0.618v

[oxidation]

2H+ + 2e- = H2, pH = 1, E = -0.0592pH = -0.0592v [reduction]

O2 + 4H+ + 4e- = 2H2O, Eo = 1.229v, E = 1.170 [reduction]
Cl2 + 2e- = 2Cl- ; Eo = 1.358; for p(Cl2) = 0, [Cl-] = 1 [no reduction]
Na+ + 1e- = Na; Eo = -2.71v; for [Na+] = 1 [no Na, no oxidation]
2-8. A student [probably polymers specialty] suggests that two possible
reactions for Problem 2.7 are:
Cl2 + 2e- = 2Cl- and Na = Na+ + e-
Do you agree with either or both? If so, what assumptions must
you make?

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For Cl2 + 2e- = 2Cl-, as written, for Cl2 to re reduced, there must be
a concentration [pressure] of Cl2 and Cl- ion to establish a Nernst
potential more positive than the prevailing electrode potential [>
-0.182v]. This means that [from rearrangement of the Nernst
equation for Cl2 reduction] the ratio of [Cl-]/p(Cl2) must be less
than or equal to 1.06x10 52 for Cl2 to reduced as written. Of course,
if p(Cl2) = 0 and [Cl-] = 1, the Nernst potential for the reduction of
Cl2 would increase to + infinity and Cl- would be oxidized until an
equilibrium pressure of Cl2 were established [p(Cl2) ~10-52 atm]!!!

For Na+ + 1e- = Na, Eo = -2.71, @ [Na+] = 1, E = -2.71v. In order

for Na+ to be reduced, the Nernst potential for Na+ reduction would
have to be increased to -0.182v, requiring a Na+ concentration,
[Na+], to be no less than 5.04x10 42 M!!!! The solubility of NaCl in
cold water, by the way, is 357 g/liter , ~ 10M......