(a) Can endothermic chemical reactions be spontaneous? (b) Can a process be spontaneous at one temperature and nonspontaneous at a different temperature? (c) Water can be decomposed to form hydrogen and oxygen, and the hydrogen and oxygen can be recombined to form water. Does this mean that the processes are thermodynamically reversible? (d) Does the amount of work that a system can doon its Id on the nath of the nrocese?

Short Answer

Expert verified
(a) Yes, endothermic chemical reactions can be spontaneous if the increase in entropy (\( ∆S \)) is large enough to overcome the positive enthalpy change (\( ∆H \)), resulting in a negative Gibbs free energy (\( ∆G \)). This is more likely to occur at higher temperatures due to the temperature-entropy term in the Gibbs free energy equation. (b) Yes, a process can be spontaneous at one temperature and nonspontaneous at a different temperature, as the Gibbs free energy (\( ∆G \)) is influenced by both enthalpy (\( ∆H \)) and entropy (\( ∆S \)) changes, as well as temperature (T). (c) The decomposition and recombination of water into hydrogen and oxygen are not thermodynamically reversible processes, as they have finite rates and energy losses and cannot fully reverse with no change to the system and its surroundings. (d) Yes, the amount of work that a system can do depends on the path of the process. Different process paths can lead to different conversion efficiencies and energy available for work, resulting in different amounts of work being done for the same initial and final states of a system.

Step by step solution

01

(Question a: Endothermic Spontaneity)

(An endothermic reaction is one where energy is absorbed from the surroundings during the reaction. Spontaneity refers to whether a reaction will occur on its own without any external intervention. For a reaction to be spontaneous, its Gibbs free energy (\( ∆G \)) must be negative. The key to answering this question is to recall the relationship between Gibbs free energy (\( ∆G \)), entropy (\( ∆S \)), and enthalpy (\( ∆H \)): \[ ∆G = ∆H - T∆S \] where T is the temperature in Kelvin.)
02

(Answer a: Endothermic Spontaneity)

(Yes, endothermic chemical reactions can be spontaneous if the increase in entropy (\( ∆S \)) is large enough to overcome the positive enthalpy change (\( ∆H \)), resulting in a negative Gibbs free energy (\( ∆G \)). This is more likely to occur at higher temperatures since the entropy term is multiplied by the temperature (T) in the Gibbs free energy equation.)
03

(Question b: Spontaneity and Temperature)

(This question focuses on understanding whether a process can have different spontaneity characteristics at different temperatures. To answer this question, we need to consider how the relation between Gibbs free energy (\( ∆G \)), entropy (\( ∆S \)), and enthalpy (\( ∆H \)) can be affected by changes in temperature.)
04

(Answer b: Spontaneity and Temperature)

(Yes, a process can be spontaneous at one temperature and nonspontaneous at a different temperature. This is because the Gibbs free energy (\( ∆G \)) is influenced by both enthalpy (\( ∆H \)) and entropy (\( ∆S \)) changes, as well as temperature (T). As temperature changes, the contribution from the temperature-entropy term (\( T∆S \)) in the \( ∆G = ∆H - T∆S \) equation can change the overall sign of Gibbs free energy, leading to a change in spontaneity.)
05

(Question c: Reversible Processes)

(This question asks whether water decomposition and recombination processes are thermodynamically reversible or not. To answer this, we need to understand the concept of thermodynamic reversibility and how it relates to the given processes.)
06

(Answer c: Reversible Processes)

(Although water can be decomposed into hydrogen and oxygen, and hydrogen and oxygen can be recombined to form water, this does not mean that both processes are thermodynamically reversible. A thermodynamically reversible process is an idealized process that occurs infinitely slowly and can be reversed with no change to the system and its surroundings. The decomposition and recombination of water are real processes with finite rates and energy losses; therefore, they are not thermodynamically reversible processes.)
07

(Question d: Work Done on the System)

(The question asks about the dependency of the amount of work that a system can do on the path of the process. The answer lies in understanding the relationship between work, energy, and the specifics of a system's path in a process.)
08

(Answer d: Work Done on the System)

(Yes, the amount of work that a system can do depends on the path of the process. A system can do work when it converts internal energy into other forms of energy. However, the conversion efficiency and the energy available to do work can differ for different process paths, resulting in different amounts of work being done for the same initial and final states of a system.)

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Most popular questions from this chapter

The value of \(K_{a}\) for nitrous acid \(\left(\mathrm{HNO}_{2}\right)\) at \(25^{\circ} \mathrm{C}\) is given in Appendix D. (a) Write the chemical equation for the equilibrium that corresponds to \(K_{a}\). (b) By using the value of \(K_{a}\) calculate \(\Delta G^{\circ}\) for the dissociation of nitrous acid in aqueous solution. (c) What is the value of \(\Delta G\) at equilibrium? (d) What is the value of \(\Delta G\) when $\left[\mathrm{H}^{+}\right]=5.0 \times 10^{-2} \mathrm{M}\(, \)\left[\mathrm{NO}_{2}^{-}\right]=6.0 \times 10^{-4} \mathrm{M},\( and \)\left[\mathrm{HNO}_{2}\right]=0.20 \mathrm{M} ?$

Carbon disulfide \(\left(C S_{2}\right)\) is a toxic, highly flammable substance. The following thermodynamic data are available for \(\mathrm{CS}_{2}(I)\) and \(\mathrm{CS}_{2}(g)\) at \(298 \mathrm{~K}\) \begin{tabular}{lcc} \hline & \(\Delta H_{i}(\mathrm{k} / \mathrm{mol})\) & $\Delta G_{i}^{\prime}(\mathrm{kJ} / \mathrm{mol})$ \\ \hline\(C S_{2}(l)\) & 89.7 & 65.3 \\ \(C S_{2}(g)\) & 117.4 & 67.2 \\ \hline \end{tabular} (a) Draw the Lewis structure of the molecule. What do you predict for the bond order of the \(\mathrm{C}-\mathrm{S}\) bonds? \((\mathbf{b})\) Use the VSEPR method to predict the structure of the \(\mathrm{CS}_{2}\) molecule. (c) Liquid \(\mathrm{CS}_{2}\) burns in \(\mathrm{O}_{2}\) with a blue flame, forming \(\mathrm{CO}_{2}(g)\) and \(\mathrm{SO}_{2}(g)\). Write a balanced equation for this reaction. (d) Using the data in the preceding table and in Appendix \(C,\) calculate \(\Delta H^{\circ}\) and \(\Delta G^{\circ}\) for the reaction in part \((c) .\) Is the reaction exothermic? Is it spontaneous at \(298 \mathrm{~K} ?\) (e) Use the data in the table to calculate \(\Delta S^{\circ}\) at $298 \mathrm{~K}\( for the vaporization of \)\mathrm{CS}_{2}(I) .$ Is the sign of \(\Delta S^{\circ}\) as you would expect for a vaporization? (f) Using data in the table and your answer to part (e), estimate the boiling point of \(\mathrm{CS}_{2}(l)\). Do you predict that the substance will be a liquid or a gas at \(298 \mathrm{~K}\) and \(101.3 \mathrm{kPa}\) ?

A certain reaction has \(\Delta H^{\circ}=+20.0 \mathrm{~kJ}\) and $\Delta S^{\circ}=\( \)+100.0 \mathrm{~J} / \mathrm{K} .$ (a) Does the reaction lead to an increase or decrease in the randomness or disorder of the system? (b) Does the reaction lead to an increase or decrease in the randomness or disorder of the surroundings? (c) Calculate \(\Delta G^{\circ}\) for the reaction at $298 \mathrm{~K} .(\mathbf{d})\( Is the reaction spontaneous at \)298 \mathrm{~K}$ under standard conditions?

Use data from Appendix \(C\) to calculate the equilibrium constant, \(K,\) and \(\Delta G^{\circ}\) at \(298 \mathrm{~K}\) for each of the following reactions: (a) \(\mathrm{H}_{2}(g)+\mathrm{I}_{2}(g) \rightleftharpoons 2 \mathrm{HI}(g)\) (b) $\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{OH}(g) \rightleftharpoons \mathrm{C}_{2} \mathrm{H}_{4}(g)+\mathrm{H}_{2} \mathrm{O}(g)$ (c) $3 \mathrm{C}_{2} \mathrm{H}_{2}(g) \rightleftharpoons \mathrm{C}_{6} \mathrm{H}_{6}(g)$

(a) For each of the following reactions, predict the sign of \(\Delta H^{*}\) and \(\Delta S^{\circ}\) without doing any calculations. (b) Based on your general chemical knowledge, predict which of these reactions will have \(K>1\) at \(25^{\circ} \mathrm{C} .(\mathbf{c})\) In each case, indicate whether \(K\) should increase or decrease with increasing temperature. (i) \(2 \mathrm{Fe}(s)+\mathrm{O}_{2}(g) \rightleftharpoons 2 \mathrm{FeO}(s)\) (ii) \(\mathrm{Cl}_{2}(g) \rightleftharpoons 2 \mathrm{Cl}(g)\) (iii) $\mathrm{NH}_{4} \mathrm{Cl}(s) \rightleftharpoons \mathrm{NH}_{3}(g)+\mathrm{HCl}(g)$ (iv) $\mathrm{CO}_{2}(\mathrm{~g})+\mathrm{CaO}(s) \rightleftharpoons \mathrm{CaCO}_{3}(s)$

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