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Ch.19 - Chemical Thermodynamics
Chapter 19, Problem 102

At what temperatures is the following reaction, the reduction of magnetite by graphite to elemental iron, spontaneous? Fe3O4(s) + 2 C(s, graphite) → 2 CO2(g) + 3 Fe(s)

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Identify the reaction and write it down in a balanced chemical equation format: \( \text{Fe}_3\text{O}_4(s) + 2\text{C}(s, \text{graphite}) \rightarrow 2\text{CO}_2(g) + 3\text{Fe}(s) \).
Determine the standard Gibbs free energy change (\( \Delta G^\circ \)) for the reaction using standard Gibbs free energies of formation for each compound involved in the reaction.
Use the equation \( \Delta G = \Delta G^\circ + RT \ln Q \) to relate the Gibbs free energy change at any temperature (T) and reaction quotient (Q). For spontaneity, \( \Delta G \) should be less than zero.
Since the reaction involves only solids and gases at standard state, the reaction quotient (Q) simplifies to 1 under standard conditions. Thus, the spontaneity depends solely on \( \Delta G^\circ \).
Calculate the temperature at which \( \Delta G^\circ \) changes sign using the relationship \( \Delta G^\circ = -RT \ln K \), where K is the equilibrium constant. The reaction is spontaneous at temperatures where \( \Delta G^\circ < 0 \).

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Key Concepts

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

Gibbs Free Energy

Gibbs Free Energy (G) is a thermodynamic potential that helps predict the spontaneity of a reaction at constant temperature and pressure. A reaction is spontaneous when the change in Gibbs Free Energy (ΔG) is negative. The relationship between ΔG, enthalpy (ΔH), and entropy (ΔS) is given by the equation ΔG = ΔH - TΔS, where T is the temperature in Kelvin.
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Entropy and Enthalpy

Entropy (S) is a measure of the disorder or randomness in a system, while enthalpy (H) is a measure of the total energy of a system, including internal energy and the energy required to make room for it. In the context of a reaction, an increase in entropy (positive ΔS) often favors spontaneity, especially at higher temperatures, while a decrease in enthalpy (negative ΔH) also promotes spontaneity.
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Temperature's Role in Spontaneity

Temperature plays a crucial role in determining the spontaneity of a reaction through its influence on the Gibbs Free Energy equation. As temperature increases, the TΔS term becomes more significant, which can make a reaction spontaneous if ΔS is positive. Therefore, understanding how temperature affects the balance between enthalpy and entropy is essential for predicting the spontaneity of the reduction of magnetite by graphite.
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Related Practice
Textbook Question

(c) In each case, indicate whether K should increase or decrease with increasing temperature. (i) 2 Mg(s) + O2 (g) ⇌ 2 MgO(s) (ii) 2 KI(s) ⇌ 2 K(g) + I2(g) (iii) Na2(g) ⇌ 2 Na(g) (iv) 2 V2O5(s) ⇌ 4 V(s) + 5 O2(g)

Textbook Question

The conversion of natural gas, which is mostly methane, into products that contain two or more carbon atoms, such as ethane (C2H6), is a very important industrial chemical process. In principle, methane can be converted into ethane and hydrogen: 2 CH4(g) → C2H6(g) + H2(g) In practice, this reaction is carried out in the presence of oxygen: 2 CH4(g) + 12 O2(g) → C2H6(g) + H2O(g) (b) Is the difference in ΔG° for the two reactions due primarily to the enthalpy term (ΔH) or the entropy term (-TΔS)?

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Textbook Question

The potassium-ion concentration in blood plasma is about 5.0⨉10-3 M, whereas the concentration in muscle-cell fluid is much greater (0.15 M ). The plasma and intracellular fluid are separated by the cell membrane, which we assume is permeable only to K+. (a) What is ΔG for the transfer of 1 mol of K+ from blood plasma to the cellular fluid at body temperature 37 °C? (b) What is the minimum amount of work that must be used to transfer this K+?

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Textbook Question

Consider the following equilibrium: N2O4(g) ⇌ 2 NO2(g) Thermodynamic data on these gases are given in Appendix C. You may assume that ΔH° and ΔS° do not vary with temperature. (a) At what temperature will an equilibrium mixture contain equal amounts of the two gases?

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Textbook Question

The reaction SO2(g) + 2 H2S(g) ⇌ 3 S(s) + 2 H2O(g) is the basis of a suggested method for removal of SO2 from power-plant stack gases. The standard free energy of each substance is given in Appendix C. (a) What is the equilibrium constant for the reaction at 298 K? (c) If PSO2 = PH2S and the vapor pressure of water is 25 torr, calculate the equilibrium SO2 pressure in the system at 298 K.

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Textbook Question

The reaction SO2(g) + 2 H2S(g) ⇌ 3 S(s) + 2 H2O(g) is the basis of a suggested method for removal of SO2 from power-plant stack gases. The standard free energy of each substance is given in Appendix C. (b) In principle, is this reaction a feasible method of removing SO2?

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