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Ch.19 - Electrochemistry
Chapter 19, Problem 165

We've said that the +1 oxidation state is uncommon for indium but is the most stable state for thallium. Verify this statement by calculating E ° and ΔG ° (in kilojoules) for the disproportionation reaction
3 M+1aq2S M3+1aq2 + 2 M1s2 M = In or Tl
Is disproportionation a spontaneous reaction for In+ and/orTl+? Standard reduction potentials for the relevant halfreactions are
In3+1aq2 + 2 e- S In+1aq2 E° = -0.44 V
In+1aq2 + e- S In1s2 E° = -0.14 V
Tl3+1aq2 + 2 e- S Tl+1aq2 E° = +1.25 V
Tl+1aq2 + e- S Tl1s2 E° = -0.34 V

Verified step by step guidance
1
Identify the disproportionation reaction: 3 M^{+1}_{(aq)} \rightarrow M^{3+}_{(aq)} + 2 M_{(s)}.
Write the half-reactions for the disproportionation: \text{Oxidation: } M^{+1}_{(aq)} \rightarrow M^{3+}_{(aq)} + 2e^- and \text{Reduction: } M^{+1}_{(aq)} + e^- \rightarrow M_{(s)}.
Calculate the standard cell potential (E^\circ_{cell}) for the disproportionation reaction using E^\circ_{cell} = E^\circ_{reduction} - E^\circ_{oxidation}.
Use the Nernst equation to calculate \Delta G^\circ: \Delta G^\circ = -nFE^\circ_{cell}, where n is the number of moles of electrons transferred and F is the Faraday constant.
Determine if the reaction is spontaneous by checking if \Delta G^\circ is negative. If \Delta G^\circ < 0, the reaction is spontaneous.

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Key Concepts

Here are the essential concepts you must grasp in order to answer the question correctly.

Oxidation States

Oxidation states indicate the degree of oxidation of an atom in a compound, reflecting the number of electrons lost or gained. For indium (In) and thallium (Tl), the +1 oxidation state is less stable for In due to its position in the periodic table, while it is more stable for Tl. Understanding these oxidation states is crucial for predicting the behavior of these elements in redox reactions.
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Disproportionation Reaction

A disproportionation reaction is a specific type of redox reaction where a single substance is simultaneously oxidized and reduced, resulting in two different products. In this case, the +1 oxidation state of In or Tl is being analyzed for its stability and tendency to undergo disproportionation. Evaluating the spontaneity of this reaction involves calculating the standard cell potential and Gibbs free energy change.
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Standard Reduction Potentials

Standard reduction potentials (E°) quantify the tendency of a chemical species to gain electrons and be reduced. These values are essential for determining the feasibility of redox reactions, including disproportionation. By comparing the E° values for the relevant half-reactions of In and Tl, one can assess whether the overall reaction is spontaneous, which is indicated by a positive cell potential.
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Related Practice
Textbook Question

The half-reactions that occur in ordinary alkaline batteries can be written as In 1999, researchers in Israel reported a new type of alkaline battery, called a 'super-iron' battery. This battery uses the same anode reaction as an ordinary alkaline battery but involves the reduction of FeO42- ion (from K2FeO4) to solid Fe(OH)3 at the cathode. (c) A super-iron battery should last longer than an ordinary alkaline battery of the same size and weight because its cathode can provide more charge per unit mass. Quan-titatively compare the number of coulombs of charge released by the reduction of 10.0 g K2FeO4 to Fe(OH)3 with the number of coulombs of charge released by the reduction 10.0 g of MnO2 to MnO(OH).

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Textbook Question
Gold metal is extracted from its ore by treating the crushed rock with an aerated cyanide solution. The unbalanced equation for the reaction is (b) Use any of the following data at 25 °C to calculate ∆G° for this reaction at 25 °C: Kf for Au(CN)2- = 6.2 x 10^38, Ka for HCN = 4.9 x 10^-10, and standard reduction potentials are
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Textbook Question
Consider the redox titration of 100.0 mL of a solution of 0.010 M Fe2+ in 1.50 M H2SO4 with a 0.010 M solution of KMnO4, yielding Fe3+ and Mn2+. The titration is carried out in an electrochemical cell equipped with a platinum electrode and a calomel reference electrode consisting of an Hg2Cl2/Hg electrode in contract with a saturated KCl solution having [Cl-] = 2.9M. Using any data in Appendixes C and D, calculate the cell potential after addition of (a) 5.0 mL, (b) 10.0mL, (c) 19.0 mL, and (d) 21.0 mL of the KMnO4 solution.
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