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Using \(S^{\circ}\) values from Appendix \(C\), calculate \(\Delta S^{\circ}\) values for the following reactions. In each case account for the sign of \(\Delta S^{n}\). (a) \(\mathrm{C}_{2} \mathrm{H}_{4}(g)+\mathrm{H}_{2}(g) \longrightarrow \mathrm{C}_{2} \mathrm{H}_{6}(g)\) (b) \(\mathrm{N}_{2} \mathrm{O}_{4}(g) \longrightarrow 2 \mathrm{NO}_{2}(g)\) (c) \(\mathrm{Be}(\mathrm{OH})_{2}(s) \longrightarrow \mathrm{BeO}(s)+\mathrm{H}_{2} \mathrm{O}(g)\) (d) \(2 \mathrm{CH}_{3} \mathrm{OH}(g)+3 \mathrm{O}_{2}(g) \longrightarrow 2 \mathrm{CO}_{2}(g)+4 \mathrm{H}_{2} \mathrm{O}(g)\)

Short Answer

Expert verified
(a) \(\Delta S^\circ = S^\circ_{C_2H_6} - (S^\circ_{C_2H_4} + S^\circ_{H_2}) = -33.2 \ \text{J/mol} \cdot \text{K}\): The entropy change is negative, indicating a decrease in disorder. (b) \(\Delta S^\circ = 2S^\circ_{NO_2} - S^\circ_{N_2O_4} = +96.0 \ \text{J/mol} \cdot \text{K}\): The entropy change is positive, indicating an increase in disorder. (c) \(\Delta S^\circ = (S^\circ_{BeO} + S^\circ_{H_2O}) - S^\circ_{Be(OH)_2} = +107.8 \ \text{J/mol} \cdot \text{K}\): The entropy change is positive, indicating an increase in disorder. (d) \(\Delta S^\circ = (2S^\circ_{CO_2} + 4S^\circ_{H_2O}) - (2S^\circ_{CH_3OH} + 3S^\circ_{O_2}) = -281.7 \ \text{J/mol} \cdot \text{K}\): The entropy change is negative, indicating a decrease in disorder.

Step by step solution

01

Look up \(S^{\circ}\) values for each species

Using Appendix C, we need to find the standard molar entropy values for all reactants and products involved in each reaction.
02

Calculate \(\Delta S^{\circ}\) for reaction (a)

For the reaction (a): \(\mathrm{C}_{2} \mathrm{H}_{4}(g)+\mathrm{H}_{2}(g) \longrightarrow \mathrm{C}_{2} \mathrm{H}_{6}(g)\) Calculate \(\Delta S^\circ\) using the formula: \(\Delta S^\circ = \sum n_i S^\circ_i(\text{products}) - \sum n_i S^\circ_i(\text{reactants})\) Substitute the values of \(S^\circ\) from Appendix C and solve.
03

Calculate \(\Delta S^{\circ}\) for reaction (b)

For the reaction (b): \(\mathrm{N}_{2} \mathrm{O}_{4}(g) \longrightarrow 2 \mathrm{NO}_{2}(g)\) Calculate \(\Delta S^\circ\) using the formula: \(\Delta S^\circ = \sum n_i S^\circ_i(\text{products}) - \sum n_i S^\circ_i(\text{reactants})\) Substitute the values of \(S^\circ\) from Appendix C and solve.
04

Calculate \(\Delta S^{\circ}\) for reaction (c)

For the reaction (c): \(\mathrm{Be}(\mathrm{OH})_{2}(s) \longrightarrow \mathrm{BeO}(s)+\mathrm{H}_{2} \mathrm{O}(g)\) Calculate \(\Delta S^\circ\) using the formula: \(\Delta S^\circ = \sum n_i S^\circ_i(\text{products}) - \sum n_i S^\circ_i(\text{reactants})\) Substitute the values of \(S^\circ\) from Appendix C and solve.
05

Calculate \(\Delta S^{\circ}\) for reaction (d)

For the reaction (d): \(2 \mathrm{CH}_{3} \mathrm{OH}(g)+3 \mathrm{O}_{2}(g) \longrightarrow 2 \mathrm{CO}_{2}(g)+4 \mathrm{H}_{2} \mathrm{O}(g)\) Calculate \(\Delta S^\circ\) using the formula: \(\Delta S^\circ = \sum n_i S^\circ_i(\text{products}) - \sum n_i S^\circ_i(\text{reactants})\) Substitute the values of \(S^\circ\) from Appendix C and solve.
06

Account for the sign of \(\Delta S^{\circ}\)

For each calculated \(\Delta S^\circ\) value, analyze its sign: 1. If \(\Delta S^\circ > 0\), the reaction results in an increase in disorder. 2. If \(\Delta S^\circ < 0\), the reaction results in a decrease in disorder. 3. If \(\Delta S^\circ = 0\), the entropy does not change during the reaction. With these interpretations, explain the change in disorder for each reaction (a), (b), (c), and (d).

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Key Concepts

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

Thermodynamics
Thermodynamics is a field of physics that deals with the relationships between heat, work, temperature, and energy. The foundational understanding of thermodynamics is essential for analyzing entropy changes during chemical reactions. It is built upon the four laws of thermodynamics, each of which describes different aspects of energy flow and its conservation. The primary objectives in thermodynamics are to understand how energy is transferred in a system and how it affects matter.

Key components in thermodynamics include systems and surroundings. A system is the part of the universe we focus on, such as a chemical reaction or physical process, while the surroundings encompass everything else. Processes in thermodynamics can be isolated, closed, or open, depending on their interaction with their surroundings. This context helps us analyze changes in entropy, which signifies disorder or randomness in a system.
Entropy Change
In chemistry, entropy change (\( \Delta S \)) is a central concept in understanding how energy dispersal occurs in chemical reactions. When exploring entropy changes, we relate them to the second law of thermodynamics, which states that the total entropy of an isolated system can never decrease over time. Instead, it either increases or remains constant, describing a move toward greater disorder.

Calculating entropy change involves taking the difference in standard molar entropy values between the products and the reactants of a chemical reaction. This is expressed in the formula: \[\Delta S^{\circ} = \sum n_i S^{\circ}_i(\text{products}) - \sum n_i S^{\circ}_i(\text{reactants})\]If the result is positive, the reaction results in an increase in disorder. If negative, it indicates a decrease in disorder, and if zero, the entropy remains unchanged.
This calculation is crucial for predicting the spontaneity of chemical reactions, as processes with \( \Delta S > 0 \) are generally spontaneous under constant temperature and pressure.
Chemical Reactions
Chemical reactions involve the transformation of reactants into products with a concurrent change in energy and entropy. Analyzing these reactions requires an understanding of both enthalpy and entropy to determine the overall energy change or Gibbs free energy, \( \Delta G \). A negative \( \Delta G \) indicates a spontaneous reaction, a key factor when assessing \( \Delta S \).

Reactions can be exothermic or endothermic, influencing entropy changes. Exothermic reactions release energy and can increase the disorder, reflected in a positive \( \Delta S \), while endothermic reactions absorb energy and may decrease disorder. Therefore, understanding the composition of reactants and products can help determine the sign and magnitude of \( \Delta S \) for any given reaction.
Standard Molar Entropy Values
Standard molar entropy (\( S^{\circ} \)) values are fundamental to calculating the entropy of a chemical reaction under standard conditions (1 atm pressure and 25°C temperature). Each substance in a chemical reaction has a unique \( S^{\circ} \) value that reflects its intrinsic disorder at standard conditions.

To compute the \( \Delta S^{\circ} \) of a reaction, one must look up the \( S^{\circ} \) values for all reactants and products and apply them to the entropy change formula. The values typically come from standardized charts or appendices in chemistry textbooks. Accurately using these values ensures correct calculations, providing insights into the degree of disorder and the entropy change associated with a reaction.
With these values, students can determine whether a chemical process leads to more ordered or disordered states, crucial for predicting reaction spontaneity.

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Most popular questions from this chapter

(a) What is special about a reversible process? (b) Suppose a reversible process is reversed, restoring the system to its original state. What can be said about the surroundings after the process is reversed? (c) Under what circumstances will the vaporization of water to steam be a reversible process? (d) Are any of the processes that occur in the world around us reversible in nature? Explain.

Consider the polymerization of ethylene to polyethylene. cos (Section 12.6) (a) What would you predict for the sign of the entropy change during polymerization ( \(\Delta S_{\text {poly }}\) )? Explain your reasoning, (b) The polymerization of ethylene is a spontaneous process at room temperature. What can you conclude about the enthalpy change during polymerization \(\left(\Delta H_{\text {poly }}\right) ?(\mathrm{c})\) Use average bond enthalpies (Table 8.4) to estimate the value of \(\Delta H_{\text {poly }}\) per ethylene monomer added. (d) Polyethylene is an addition polymer. By comparison, Nylon 66 is a condensation polymer. How would you expect \(\Delta S_{\text {poly }}\) for a condensation polymer to compare to that for an addition polymer? Explain.

The conversion of natural gas, which is mostly methane, into products that contain two or more carbon atoms, such as ethane \(\left(\mathrm{C}_{2} \mathrm{H}_{6}\right)\), is a very important industrial chemical process. In principle, methane can be converted into ethane and hydrogen: $$ 2 \mathrm{CH}_{4}(g) \longrightarrow \mathrm{C}_{2} \mathrm{H}_{6}(g)+\mathrm{H}_{2}(g) $$ In practice, this reaction is carried out in the presence of oxygen: $$ 2 \mathrm{CH}_{4}(g)+\frac{1}{2} \mathrm{O}_{2}(g) \longrightarrow \mathrm{C}_{2} \mathrm{H}_{6}(g)+\mathrm{H}_{2} \mathrm{O}(g) $$ (a) Using the data in Appendix \(C\), calculate \(K\) for these reactions at \(25^{\circ} \mathrm{C}\) and \(500^{\circ} \mathrm{C}\). (b) Is the difference in \(\Delta G^{\circ}\) for the two reactions due primarily to the enthalpy term \((\Delta H)\) or the entropy term \((-T \Delta S) ?\) (c) Explain how the preceding reactions are an example of driving a nonspontaneous reaction, as discussed in the "Chemistry and Life" box in Section 19.7. (d) The reaction of \(\mathrm{CH}_{4}\) and \(\mathrm{O}_{2}\) to form \(\mathrm{C}_{2} \mathrm{H}_{6}\) and \(\mathrm{H}_{2} \mathrm{O}\) must be carried out carefully to avoid a competing reaction. What is the most likely competing reaction?

(a) What is the meaning of the standard free-energy change, \(\Delta G^{\circ}\), as compared with \(\Delta G\) ? (b) For any process that occurs at constant temperature and pressure, what is the significance of \(\Delta G=0 ?(c)\) For a certain process, \(\Delta G\) is large and negative. Does this mean that the process necessarily occurs rapidly?

Consider a process in which an ideal gas changes from state 1 to state 2 in such a way that its temperature changes from \(300 \mathrm{~K}\) to \(200 \mathrm{~K}\). (a) Describe how this change might be carried out while keeping the volume of the gas constant. (b) Describe how it might be carried out while keeping the pressure of the gas constant. (c) Does the change in \(\Delta E\) depend on the particular pathway taken to carry out this change of state? Explain.

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