Chapter 19: Problem 86
Ammonium nitrate dissolves spontaneously and endothermally in water at room temperature. What can you deduce about the sign of \(\Delta S\) for this solution process?
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Chapter 19: Problem 86
Ammonium nitrate dissolves spontaneously and endothermally in water at room temperature. What can you deduce about the sign of \(\Delta S\) for this solution process?
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Suppose we vaporize a mole of liquid water at \(25^{\circ} \mathrm{C}\) and another mole of water at \(100{ }^{\circ} \mathrm{C}\). (a) Assuming that the enthalpy of vaporization of water does not change much between \(25^{\circ} \mathrm{C}\) and \(100^{\circ} \mathrm{C}\), which process involves the larger change in entropy? (b) Does the entropy change in either process depend on whether we carry out the process reversibly or not? Explain.
Calculate \(\Delta S^{\circ}\) values for the following reactions by using tabulated \(S^{\circ}\) values from Appendix \(C\). In each case explain the sign of \(\Delta S^{\circ}\). (a) \(\mathrm{N}_{2} \mathrm{H}_{4}(\mathrm{~g})+\mathrm{H}_{2}(\mathrm{~g}) \longrightarrow 2 \mathrm{NH}_{3}(g)\) (b) \(\mathrm{K}(s)+\mathrm{O}_{2}(g) \longrightarrow \mathrm{KO}_{2}(s)\) (c) \(\mathrm{Mg}(\mathrm{OH})_{2}(s)+2 \mathrm{HCl}(\mathrm{g}) \longrightarrow \mathrm{MgCl}_{2}(s)+2 \mathrm{H}_{2} \mathrm{O}(l)\) (d) \(\mathrm{CO}(g)+2 \mathrm{H}_{2}(g) \longrightarrow \mathrm{CH}_{3} \mathrm{OH}(g)\)
One way to derive Equation \(19.3\) depends on the observation that at constant \(T\) the number of ways, \(W\), of arranging \(m\) ideal-gas particles in a volume \(V\) is proportional to the volume raised to the \(m\) power: \(W \propto V^{m}\) Use this relationship and Boltzmann's relationship between entropy and number of arrangements (Equation 19.5) to derive the equation for the entropy change for the isothermal expansion or compression of \(n\) moles of an ideal gas.
Consider the polymerization of ethylene to polyethylene. (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 \(\left(\Delta H_{\text {poly }}\right)\) ? (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 relationship between the temperature of a reaction, its standard enthalpy change, and the equilibrium constant at that temperature can be expressed as the following linear equation: $$ \mathrm{n} K=\frac{-\Delta H^{\circ}}{R T}+\text { constant } $$ (a) Explain how this equation can be used to determine \(\Delta H^{\circ}\) experimentally from the equilibrium constants at several different temperatures. (b) Derive the preceding equation using relationships given in this chapter. To what is the constant equal?
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