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Problem 109

Kyanite, sillimanite, and andalusite all have the…

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Problem 111

Synthesis gas, a mixture that includes the fuels CO and $\mathrm{H}_{2}$, is used to produce liquid hydrocarbons and methanol. It is made at pressures up to 100 atm by oxidation of methane followed by the steam reforming and water-gas shift reactions. Because the process is exothermic, temperatures reach $950-1100^{\circ} \mathrm{C}$, and the conditions are such that the amounts of $\mathrm{H}_{2}, \mathrm{CO}, \mathrm{CO}_{2}, \mathrm{CH}_{4}$, and $\mathrm{H}_{2} \mathrm{O}$ leaving the reactor are close to the equilibrium amounts for the steam re-forming and water-gas shift reactions:
$$\begin{aligned} \mathrm{CH}_{4}(g)+\mathrm{H}_{2} \mathrm{O}(g) & \rightleftharpoons \mathrm{CO}(g)+3 \mathrm{H}_{2}(g) \quad \text { (steam re-forming) } \\ \mathrm{CO}(g)+\mathrm{H}_{2} \mathrm{O}(g) & \rightleftharpoons \mathrm{CO}_{2}(g)+\mathrm{H}_{2}(g) \quad \text { (water-gas shift) } \end{aligned}$$
(a) At $1000 .$ ', what are $\Delta G^{\circ}$ and $\Delta H^{\circ}$ for the steam re-forming
reaction and for the water-gas shift reaction?
(b) By doubling the steam re-forming step and adding it to the water-gas shift step, we obtain the following combined reaction:
$$2 \mathrm{CH}_{4}(g)+3 \mathrm{H}_{2} \mathrm{O}(g) \rightleftharpoons \mathrm{CO}_{2}(g)+\mathrm{CO}(g)+7 \mathrm{H}_{2}(g)$$
Is this reaction spontaneous at $1000 .^{\circ} \mathrm{C}$ in the standard state?
(c) Is it spontaneous at 98 atm and $50 . \%$ conversion (when $50 . \%$ of the starting materials have reacted)?
(d) Is it spontaneous at 98 atm and $90 . \%$ conversion?

MH
Johns Hopkins University

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Problem 108

Consider the formation of ammonia:
$$\mathrm{N}_{2}(g)+3 \mathrm{H}_{2}(g) \rightleftharpoons 2 \mathrm{NH}_{3}(g)$$
(a) Assuming that $\Delta H^{\circ}$ and $\Delta S^{\circ}$ are constant with temperature, find the temperature at which $K_{\mathrm{p}}=1.00 .$
(b) Find $K_{\mathrm{p}}$ at $400 .^{\circ} \mathrm{C}$ , a typical temperature for $\mathrm{NH}_{3}$ production.
(c) Given the lower $K_{\mathrm{p}}$ at the higher temperature, why are these conditions used industrially?

Answer
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Chapter 20
Thermodynamics: Entropy, Free Energy, and the Direction of Chemical Reactions
CHEMISTRY: The Molecular Nature of Matter and Change 2016

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