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Ch.19 - Chemical Thermodynamics
Chapter 19, Problem 111a,c

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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Identify the reaction: \( \text{SO}_2(g) + 2 \text{H}_2\text{S}(g) \rightleftharpoons 3 \text{S}(s) + 2 \text{H}_2\text{O}(g) \).
Use the standard free energy change \( \Delta G^\circ \) for the reaction, which can be calculated using \( \Delta G^\circ = \sum \Delta G^\circ_{\text{products}} - \sum \Delta G^\circ_{\text{reactants}} \).
Apply the relationship between \( \Delta G^\circ \) and the equilibrium constant \( K_p \) using the equation \( \Delta G^\circ = -RT \ln K_p \), where \( R \) is the gas constant and \( T \) is the temperature in Kelvin.
Express the equilibrium constant \( K_p \) in terms of partial pressures: \( K_p = \frac{(P_{\text{H}_2\text{O}})^2}{(P_{\text{SO}_2})(P_{\text{H}_2\text{S}})^2} \).
Given that \( P_{\text{SO}_2} = P_{\text{H}_2\text{S}} \) and \( P_{\text{H}_2\text{O}} = 25 \text{ torr} \), substitute these into the expression for \( K_p \) and solve for \( P_{\text{SO}_2} \).

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Key Concepts

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

Equilibrium Constant (K)

The equilibrium constant (K) is a numerical value that expresses the ratio of the concentrations of products to reactants at equilibrium for a given reaction at a specific temperature. For the reaction provided, K can be calculated using the partial pressures of the gases involved. Understanding K is crucial for determining how changes in pressure or concentration affect the position of equilibrium.
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Gibbs Free Energy (ΔG)

Gibbs free energy (ΔG) is a thermodynamic potential that measures the maximum reversible work obtainable from a thermodynamic system at constant temperature and pressure. The relationship between ΔG and the equilibrium constant (K) is given by the equation ΔG = -RT ln(K). This concept is essential for predicting the spontaneity of the reaction and understanding how the free energy changes with varying conditions.
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Le Chatelier's Principle

Le Chatelier's Principle states that if a dynamic equilibrium is disturbed by changing the conditions, the system will adjust itself to counteract the change and restore a new equilibrium. This principle is important in predicting how the equilibrium position will shift in response to changes in pressure, concentration, or temperature, which is relevant for calculating the equilibrium pressure of SO2 in the given reaction.
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Related Practice
Textbook Question
Carbon disulfide 1CS22 is a toxic, highly flammable substance. The following thermodynamic data are available for CS21l2 and CS21g2 at 298 K: (e) Use the data in the table to calculate ΔS° at 298 K for the vaporization of CS21l2. Is the sign of ΔS° as you would expect for a vaporization?
Textbook Question
The following data compare the standard enthalpies and free energies of formation of some crystalline ionic substances and aqueous solutions of the substances:
(a) Write the formation reaction for AgNO31s2. Based on this reaction, do you expect the entropy of the system to increase or decrease upon the formation of AgNO31s2? (b) Use ΔH°f and ΔG°f of AgNO31s2 to determine the entropy change upon formation of the substance. Is your answer consistent with your reasoning in part (a)?
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?

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?

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. (d) Would you expect the process to be more or less effective at higher temperatures?

Textbook Question

When most elastomeric polymers (e.g., a rubber band) are stretched, the molecules become more ordered, as illustrated here:

Suppose you stretch a rubber band. (a) Do you expect the entropy of the system to increase or decrease?