Chapter 17: Problem 23
Which 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.
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Chapter 17: Problem 23
Which 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.
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Hydrogen sulfide can be removed from natural gas by the reaction $$2 \mathrm{H}_{2} \mathrm{~S}(g)+\mathrm{SO}_{2}(g) \rightleftharpoons 3 \mathrm{~S}(s)+2 \mathrm{H}_{2} \mathrm{O}(g)$$ Calculate \(\Delta G^{\circ}\) and \(K\) (at \(298 \mathrm{~K}\) ) for this reaction. Would this reaction be favored at a high or low temperature?
The third law of thermodynamics states that the entropy of a perfect crystal at \(0 \mathrm{~K}\) is zero. In Appendix \(4, \mathrm{~F}^{-}(a q), \mathrm{OH}^{-}(a q)\), and \(\mathrm{S}^{2-}(a q)\) all have negative standard entropy values. How can \(S^{\circ}\) values be less than zero?
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 temperature dependent. Predict the sign of \(\Delta S_{\text {sarr }}\) for this reaction. Explain. c. For \(\mathrm{Ni}(\mathrm{CO})_{4}(g), \Delta H_{\mathrm{f}}^{\circ}=-607 \mathrm{~kJ} / \mathrm{mol}\) and \(S^{\circ}=417 \mathrm{~J} / \mathrm{K} \cdot \mathrm{mol}\) 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 \(\mathrm{CO}(\mathrm{g})\) 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 preceding 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 \(29.0 \mathrm{~kJ} / \mathrm{mol}\).
At 1 atm, liquid water is heated above \(100^{\circ} \mathrm{C}\). For this process, which of the following choices (i-iv) is correct for \(\Delta S_{\text {sur }}\) ? \(\Delta S\) ? \(\Delta S_{\text {univ }} ?\) Explain each answer. i. greater than zero ii. less than zero iii. equal to zero iv. cannot be determined
The enthalpy of vaporization of chloroform \(\left(\mathrm{CHCl}_{3}\right)\) is \(31.4\) \(\mathrm{kJ} / \mathrm{mol}\) at its boiling point \(\left(61.7^{\circ} \mathrm{C}\right) .\) Determine \(\Delta S_{\mathrm{sys}}, \Delta S_{\mathrm{sur}}\), and \(\Delta S_{\text {univ }}\) when \(1.00 \mathrm{~mol}\) chloroform is vaporized at \(61.7^{\circ} \mathrm{C}\) and \(1.00 \mathrm{~atm} .\)
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