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Explain why cell potentials are not multiplied by the coefficients in the balanced redox equation. (Use the relationship between \(\Delta G\) and cell potential to do this.)

Short Answer

Expert verified
Cell potentials are not multiplied by the coefficients in the balanced redox equation because reduction potentials are an intensive property, meaning they are independent of the extent of the reaction or the amount of the substance. As a result, doubling or tripling the reaction doesn't change the reduction potential. The cell potential is given by the difference between the reduction potentials of the half-reactions, and since coefficients don't affect this, they don't appear in the cell potential calculation. The number of moles of electrons transferred (n) impacts the calculation of Gibbs free energy (\(\Delta G\)) in the relationship \(\Delta G = -nFE_{cell}\), but not the cell potential itself.

Step by step solution

01

State the relationship between Gibbs free energy and cell potential

The relationship between Gibbs free energy (\(\Delta G\)) and cell potential (\(E_{cell}\)) is given by the equation: \[\Delta G = -nFE_{cell}\] where \(\Delta G\) is the Gibbs free energy, \(n\) is the number of moles of electrons transferred in the redox reaction, \(F\) is Faraday's constant (approximately 96485 C/mol), and \(E_{cell}\) is the cell potential.
02

Express cell potential as a difference of reduction potentials

Cell potential is equal to the difference between the standard reduction potentials of the half-reactions involved in the redox reaction: \[E_{cell} = E_{cathode} - E_{anode}\] Here, \(E_{cathode}\) is the reduction potential of the half-reaction occurring at the cathode, while \(E_{anode}\) is the reduction potential of the half-reaction occurring at the anode.
03

Explain why the balanced redox equation has no effect on the coefficient

In the balanced redox equation, each half-reaction is multiplied by a coefficient to ensure that the number of electrons transferred in each half-reaction is equal. However, when we look at the cell potential expression (difference between the reduction potentials), the coefficients do not appear. The reason is that the reduction potentials of half-reactions are an intensive property, meaning they are independent of the extent of the reaction or the amount of the substance. In other words, doubling or tripling the reaction (by multiplying the balanced half-reaction with a coefficient) doesn't change the reduction potential, so the coefficients will not appear when calculating the cell potential.
04

Conclude that the cell potential doesn't depend on the coefficients

Thus, we conclude that cell potentials are not multiplied by the coefficients in the balanced redox equation, since the coefficients don't affect the intensive property such as the reduction potentials. As a result, only the number of moles of electrons transferred (\(n\)) impacts the calculation of Gibbs free energy in the relationship between \(\Delta G\) and \(E_{cell}\), but not the cell potential itself.

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Most popular questions from this chapter

The free energy change for a reaction, \(\Delta G\), is an extensive property. What is an extensive property? Surprisingly, one can calculate \(\Delta G\) from the cell potential, \(\mathscr{b}\), for the reaction. This is surprising because \(\mathscr{B}\) is an intensive property. How can the extensive property \(\Delta G\) be calculated from the intensive property \(\mathscr{E}\) ?

Define oxidation and reduction in terms of both change in oxidation number and electron loss or gain.

Sketch the galvanic cells based on the following overall reactions. Show the direction of electron flow and identify the cathode and anode. Give the overall balanced equation. Assume that all concentrations are \(1.0 M\) and that all partial pressures are \(1.0 \mathrm{~atm}\). a. \(\mathrm{Cr}^{3+}(a q)+\mathrm{Cl}_{2}(g) \rightleftharpoons \mathrm{Cr}_{2} \mathrm{O}_{7}^{2-}(a q)+\mathrm{Cl}^{-}(a q)\) b. \(\mathrm{Cu}^{2+}(a q)+\mathrm{Mg}(s) \rightleftharpoons \mathrm{Mg}^{2+}(a q)+\mathrm{Cu}(s)\)

Consider the galvanic cell based on the following half-reactions: $$\begin{array}{ll}\mathrm{Au}^{3+}+3 \mathrm{e}^{-} \longrightarrow \mathrm{Au} & \mathscr{E}^{\circ}=1.50 \mathrm{~V} \\ \mathrm{Tl}^{+}+\mathrm{e}^{-} \longrightarrow \mathrm{Tl} & \mathscr{E}^{\circ}=-0.34 \mathrm{~V} \end{array}$$ a. Determine the overall cell reaction and calculate \(\mathscr{E}_{\mathrm{ccll}}^{\circ}\) b. Calculate \(\Delta G^{\circ}\) and \(K\) for the cell reaction at \(25^{\circ} \mathrm{C}\). c. Calculate \(\mathscr{E}_{\text {cell }}\) at \(25^{\circ} \mathrm{C}\) when \(\left[\mathrm{Au}^{3+}\right]=1.0 \times 10^{-2} M\) and \(\left[\mathrm{Tl}^{+}\right]=1.0 \times 10^{-4} \mathrm{M}\)

In making a specific galvanic cell, explain how one decides on the electrodes and the solutions to use in the cell.

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