Chapter 17: Problem 8
Is \(\Delta S_{\text {surr }}\) favorable or unfavorable for exothermic reactions? Endothermic reactions? Explain.
Chapter 17: Problem 8
Is \(\Delta S_{\text {surr }}\) favorable or unfavorable for exothermic reactions? Endothermic reactions? Explain.
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Get started for freeWhich of the following processes are spontaneous? a. Salt dissolves in \(\mathrm{H}_{2} \mathrm{O}\). b. A clear solution becomes a uniform color after a few drops of dye are added. c. Iron rusts. d. You clean your bedroom.
For the process \(\mathrm{A}(l) \longrightarrow \mathrm{A}(\mathrm{g})\), which direction is favored by changes in energy probability? Positional probability? Explain your answers. If you wanted to favor the process as written, would you raise or lower the temperature of the system? Explain.
The synthesis of glucose directly from \(\mathrm{CO}_{2}\) and \(\mathrm{H}_{2} \mathrm{O}\) and the synthesis of proteins directly from amino acids are both nonspontaneous processes under standard conditions. Yet it is necessary for these to occur for life to exist. In light of the second law of thermodynamics, how can life exist?
When the environment is contaminated by a toxic or potentially toxic substance (for example, from a chemical spill or the use of insecticides), the substance tends to disperse. How is this consistent with the second law of thermodynamics? In terms of the second law, which requires the least work: cleaning the environment after it has been contaminated or trying to prevent the contamination before it occurs? Explain.
Impure nickel, refined by smelting sulfide ores in a blast furnace, can be converted into metal from \(99.90 \%\) to \(99.99 \%\) purity by the Mond process. The primary reaction involved in the Mond process is $$ \mathrm{Ni}(s)+4 \mathrm{CO}(g) \rightleftharpoons \mathrm{Ni}(\mathrm{CO})_{4}(g) $$ a. Without referring to Appendix 4 , predict the sign of \(\Delta S^{\circ}\) for the above reaction. Explain. b. The spontaneity of the above reaction is temperaturedependent. Predict the sign of \(\Delta S_{\text {surr }}\) for this reaction. Explain. c. For \(\mathrm{Ni}(\mathrm{CO})_{4}(g), \Delta H_{\mathrm{f}}^{\circ}=-607 \mathrm{~kJ} / \mathrm{mol}\) and \(S^{\circ}=417 \mathrm{~J} / \mathrm{K}\). mol at \(298 \mathrm{~K}\). Using these values and data in Appendix 4 , calculate \(\Delta H^{\circ}\) and \(\Delta S^{\circ}\) for the above reaction. d. Calculate the temperature at which \(\Delta G^{\circ}=0(K=1)\) for the above reaction, assuming that \(\Delta H^{\circ}\) and \(\Delta S^{\circ}\) do not depend on temperature. e. The first step of the Mond process involves equilibrating impure nickel with \(\mathrm{CO}(g)\) and \(\mathrm{Ni}(\mathrm{CO})_{4}(g)\) at about \(50^{\circ} \mathrm{C}\). The purpose of this step is to convert as much nickel as possible into the gas phase. Calculate the equilibrium constant for the above reaction at \(50 .{ }^{\circ} \mathrm{C}\). f. In the second step of the Mond process, the gaseous \(\mathrm{Ni}(\mathrm{CO})_{4}\) is isolated and heated to \(227^{\circ} \mathrm{C}\). The purpose of this step is to deposit as much nickel as possible as pure solid (the reverse of the preceding reaction). Calculate the equilibrium constant for the preceding reaction at \(227^{\circ} \mathrm{C}\). g. Why is temperature increased for the second step of the Mond process? h. The Mond process relies on the volatility of \(\mathrm{Ni}(\mathrm{CO})_{4}\) for its success. Only pressures and temperatures at which \(\mathrm{Ni}(\mathrm{CO})_{4}\) is a gas are useful. A recently developed variation of the Mond process carries out the first step at higher pressures and a temperature of \(152^{\circ} \mathrm{C}\). Estimate the maximum pressure of \(\mathrm{Ni}(\mathrm{CO})_{4}(g)\) that can be attained before the gas will liquefy at \(152^{\circ} \mathrm{C}\). The boiling point for \(\mathrm{Ni}(\mathrm{CO})_{4}\) is \(42^{\circ} \mathrm{C}\) and the enthalpy of vaporization is \(29.0 \mathrm{~kJ} / \mathrm{mol}\). [Hint: The phase change reaction and the corresponding equilibrium expression are $$ \mathrm{Ni}(\mathrm{CO})_{4}(l) \rightleftharpoons \mathrm{Ni}(\mathrm{CO})_{4}(g) \quad K=P_{\mathrm{Ni}(\mathrm{CO})} $$ \(\mathrm{Ni}(\mathrm{CO})_{4}(g)\) will liquefy when the pressure of \(\mathrm{Ni}(\mathrm{CO})_{4}\) is greater than the \(K\) value.]
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