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Given the following two standard reduction potentials, $$\begin{array}{ll}{\mathrm{M}^{3+}+3 \mathrm{e}^{-} \longrightarrow \mathrm{M}} & {\mathscr{E}^{\circ}=-0.10 \mathrm{V}} \\ {\mathrm{M}^{2+}+2 \mathrm{e}^{-} \longrightarrow \mathrm{M}} & {\mathscr{E}^{\circ}=-0.50 \mathrm{V}}\end{array}$$ solve for the standard reduction potential of the half-reaction $$\mathrm{M}^{3+}+\mathrm{e}^{-} \longrightarrow \mathrm{M}^{2+}$$ (Hint: You must use the extensive property \(\Delta G^{\circ}\) to determine the standard reduction potential.)

Short Answer

Expert verified
The standard reduction potential of the half-reaction M鲁鈦 + e鈦 鈫 M虏鈦 is -0.699 V.

Step by step solution

01

Find the 鈭咷掳 for M鲁鈦 鈫 M and M虏鈦 鈫 M half-reactions

First, let's calculate the 鈭咷掳 values for both given reduction reactions using the equation: 鈭咷掳 = -nFE掳. For M鲁鈦 鈫 M: E掳 = -0.10 V; n = 3 鈭咷掳 = -(3)(96,485 C/mol)(-0.10 V) 鈭咷掳 = 29,045.5 J/mol For M虏鈦 鈫 M: E掳 = -0.50 V; n = 2 鈭咷掳 = -(2)(96,485 C/mol)(-0.50 V) 鈭咷掳 = 96,485 J/mol
02

Find the 鈭咷掳 for M鲁鈦 鈫 M虏鈦 half-reaction using given 鈭咷掳 values

We can relate the 鈭咷掳 of the reactions with the following equation: 鈭咷掳(M鲁鈦 鈫 M虏鈦) = 鈭咷掳(M虏鈦 鈫 M) - 鈭咷掳(M鲁鈦 鈫 M) 鈭咷掳(M鲁鈦 鈫 M虏鈦) = 96,485 J/mol - 29,045.5 J/mol 鈭咷掳(M鲁鈦 鈫 M虏鈦) = 67,439.5 J/mol
03

Find the standard reduction potential of M鲁鈦 鈫 M虏鈦 using the calculated 鈭咷掳

Now we can find the standard reduction potential of the required half-reaction using the equation: E掳 = -鈭咷掳/(nF) In this reaction (M鲁鈦 鈫 M虏鈦), only one electron is involved: n = 1. E掳(M鲁鈦 鈫 M虏鈦) = -67,439.5 J/mol / (1 * 96,485 C/mol) E掳(M鲁鈦 鈫 M虏鈦) = -0.699 V So, the standard reduction potential of the half-reaction M鲁鈦 + e鈦 鈫 M虏鈦 is -0.699 V.

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Key Concepts

These are the key concepts you need to understand to accurately answer the question.

Standard Reduction Potential
The standard reduction potential, often denoted as \( \mathscr{E}^{\circ} \), is a measure of the tendency of a chemical species to gain electrons and thereby be reduced. A more negative \( \mathscr{E}^{\circ} \) value indicates a lesser tendency to gain electrons. It is typically measured in volts (V), and each half-reaction has a unique value.
In our given problem, we are provided with the standard reduction potentials for two reactions involving the species \( M^{3+} \) and \( M^{2+} \). The values were \(-0.10\) V for \( M^{3+} + 3e^- \rightarrow M \) and \(-0.50\) V for \( M^{2+} + 2e^- \rightarrow M \).
These potentials are determined under standard conditions, which include 1 M concentration of ions, a pressure of 1 atm, and a temperature of 298 K, or 25 掳C. It is crucial to note that these potentials allow us to predict the direction of electron flow in electrochemical reactions.
  • Greater negative value: Less likely to be reduced.
  • Greater positive value: More likely to be reduced.
Gibbs Free Energy
Gibbs free energy, represented by \( \Delta G^{\circ} \), is a thermodynamic property that indicates the maximum reversible work that can be performed by a thermodynamic system at constant temperature and pressure. In electrochemistry, it is directly related to the cell potential and the number of electrons transferred, following the equation \( \Delta G^{\circ} = -nFE^{\circ} \), where \( n \) is the number of moles of electrons, \( F \) is the Faraday constant (approximately 96,485 C/mol), and \( E^{\circ} \) is the standard cell potential.
In the solution of this exercise, we observed the calculation of \( \Delta G^{\circ} \) for the two half-reactions given:
  • \( \Delta G^{\circ} \) for \( M^{3+} \rightarrow M \) was 29,045.5 J/mol.
  • \( \Delta G^{\circ} \) for \( M^{2+} \rightarrow M \) was 96,485 J/mol.
These values were then used to find the \( \Delta G^{\circ} \) for the half-reaction \( M^{3+} \rightarrow M^{2+} \), giving us 67,439.5 J/mol. This indicates the energy change for the process of converting \( M^{3+} \) to \( M^{2+} \), guided by the principle that systems tend to move towards lower energy states.
This property is crucial for determining the feasibility of reactions, providing an understanding of the energy changes, and whether a process is spontaneous or non-spontaneous under standard conditions.
Half-Reaction
A half-reaction is a representation of either the oxidation or reduction process in a redox reaction. Each half-reaction shows the transfer of electrons, which are involved in the overall reaction, making it a cornerstone concept in electrochemistry.
In this exercise, the two half-reactions were:
  • \( M^{3+} + 3e^- \rightarrow M \)
  • \( M^{2+} + 2e^- \rightarrow M \)
These illustrate the reduction of \( M^{3+} \) and \( M^{2+} \) ions to \( M \). The step-by-step solution required determining the half-reaction \( M^{3+} + e^- \rightarrow M^{2+} \).
By analyzing half-reactions, we can discern the direction of electron flow and the specific elements involved in gaining or losing electrons. This is foundational for calculating properties such as reduction potentials and Gibbs free energy changes and is pivotal in determining the overall cell reactions and their feasibility. Understanding these half-reactions allows chemists and engineers to predict and manipulate the behavior of electrochemical systems, including batteries and corrosion processes.

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Most popular questions from this chapter

Consider the following electrochemical cell: a. If silver metal is a product of the reaction, is the cell a galvanic cell or electrolytic cell? Label the cathode and anode, and describe the direction of the electron flow. b. If copper metal is a product of the reaction, is the cell a galvanic cell or electrolytic cell? Label the cathode and anode, and describe the direction of the electron flow. c. If the above cell is a galvanic cell, determine the standard cell potential. d. If the above cell is an electrolytic cell, determine the minimum external potential that must be applied to cause the reaction to occur.

Give the balanced cell equation and determine \(\mathscr{E}^{\circ}\) for the galvanic cells based on the following half-reactions. Standard reduction potentials are found in Table 18.1. a. \(\mathrm{Cr}_{2} \mathrm{O}_{7}^{2-}+14 \mathrm{H}^{+}+6 \mathrm{e}^{-} \rightarrow 2 \mathrm{Cr}^{3+}+7 \mathrm{H}_{2} \mathrm{O}\) \(\mathrm{H}_{2} \mathrm{O}_{2}+2 \mathrm{H}^{+}+2 \mathrm{e}^{-} \rightarrow 2 \mathrm{H}_{2} \mathrm{O}\) b. \(2 \mathrm{H}^{+}+2 \mathrm{e}^{-} \rightarrow \mathrm{H}_{2}\) \(\mathrm{Al}^{3+}+3 \mathrm{e}^{-} \rightarrow \mathrm{Al}\)

Consider the following galvanic cell at \(25^{\circ} \mathrm{C} :\) $$\text { Pt }\left|\mathrm{Cr}^{2+}(0.30 M), \mathrm{Cr}^{3+}(2.0 M)\right|\left|\mathrm{Co}^{2+}(0.20 M)\right| \mathrm{Co}$$ The overall reaction and equilibrium constant value are $$2 \mathrm{Cr}^{2+}(a q)+\mathrm{Co}^{2+}(a q) \rightleftharpoons_{2 \mathrm{Cr}^{3+}}(a q)+\mathrm{Co}(s) \quad K=2.79 \times 10^{7}$$ Calculate the cell potential, \(\mathscr{E},\) for this galvanic cell and \(\Delta G\) for the cell reaction at these conditions.

Which of the following statements concerning corrosion is(are) true? For the false statements, correct them. a. Corrosion is an example of an electrolytic process. b. Corrosion of steel involves the reduction of iron coupled with the oxidation of oxygen. c. Steel rusts more easily in the dry (arid) Southwest states than in the humid Midwest states. d. Salting roads in the winter has the added benefit of hindering the corrosion of steel. e. The key to cathodic protection is to connect via a wire a metal more easily oxidized than iron to the steel surface to be protected.

The measurement of \(\mathrm{pH}\) using a glass electrode obeys the Nernst equation. The typical response of a pH meter at \(25.00^{\circ} \mathrm{C}\) is given by the equation $$\mathscr{E}_{\text { meas }}=\mathscr{E}_{\text { ref }}+0.05916 \mathrm{pH}$$ where \(\mathscr{E}_{\text { ref }}\) contains the potential of the reference electrode and all other potentials that arise in the cell that are not related to the hydrogen ion concentration. Assume that \(\mathscr{E}_{\mathrm{ref}}=0.250 \mathrm{V}\) and that \(\mathscr{E}_{\text { meas }}=0.480 \mathrm{V}\) a. What is the uncertainty in the values of \(\mathrm{pH}\) and \(\left[\mathrm{H}^{+}\right]\) if the nncertainty in the measured potential is \(+1 \mathrm{mV}\) \(( \pm 0.001 \mathrm{V}) ?\) b. To what precision must the potential be measured for the uncertainty in \(\mathrm{pH}\) to be \(\pm 0.02 \mathrm{pH}\) unit?

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