• Home
  • Textbooks
  • General Chemistry: Principles and Modern Applications
  • Spontaneous Change: Entropy and Gibbs Energy

General Chemistry: Principles and Modern Applications

Ralph H. Petrucci, F. Geoffrey Herring, Jeffry D. Madura

Chapter 19

Spontaneous Change: Entropy and Gibbs Energy - all with Video Answers

Educators


Chapter Questions

01:45

Problem 1

Indicate whether each of the following changes represents an increase or a decrease in entropy in a system, and explain your reasoning: (a) the freezing of ethanol; (b) the sublimation of dry ice; (c) the burning of a rocket fuel.

Jesse Leeder
Jesse Leeder
Numerade Educator
02:40

Problem 2

Arrange the entropy changes of the following processes, all at $25^{\circ} \mathrm{C},$ in the expected order of increasing $\Delta S,$ and explain your reasoning:
(a) $\mathrm{H}_{2} \mathrm{O}(1,1 \mathrm{atm}) \longrightarrow \mathrm{H}_{2} \mathrm{O}(\mathrm{g}, 1 \mathrm{atm})$
(b) $\mathrm{CO}_{2}(\mathrm{s}, 1 \mathrm{atm}) \longrightarrow \mathrm{CO}_{2}(\mathrm{g}, 10 \mathrm{mm} \mathrm{Hg})$
(c) $\mathrm{H}_{2} \mathrm{O}(1,1 \mathrm{atm}) \longrightarrow \mathrm{H}_{2} \mathrm{O}(\mathrm{g}, 10 \mathrm{mmHg})$

Jesse Leeder
Jesse Leeder
Numerade Educator
02:02

Problem 3

Use ideas from this chapter to explain this famous remark attributed to Rudolf Clausius (1865)$:^{\prime \prime} \mathrm{Die}$ Energie der Welt ist konstant; die Entropie der Welt strebt einem Maximum zu." ("The energy of the world is constant; the entropy of the world increases toward a maximum.")

Alexander Clippinger
Alexander Clippinger
Numerade Educator
02:28

Problem 4

Comment on the difficulties of solving environmental pollution problems from the standpoint of entropy changes associated with the formation of pollutants and with their removal from the environment.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
05:03

Problem 5

Indicate whether the entropy of the system would increase or decrease in each of the following reactions. If you cannot be certain simply by inspecting the equation, explain why.
(a) $\mathrm{CCl}_{4}(1) \longrightarrow \mathrm{CCl}_{4}(\mathrm{g})$
(b) $\mathrm{CuSO}_{4} \cdot 3 \mathrm{H}_{2} \mathrm{O}(\mathrm{s})+2 \mathrm{H}_{2} \mathrm{O}(\mathrm{g}) \longrightarrow$
$\mathrm{CuSO}_{4} \cdot 5 \mathrm{H}_{2} \mathrm{O}(\mathrm{s})$
(c) $\mathrm{SO}_{3}(\mathrm{g})+\mathrm{H}_{2}(\mathrm{g}) \longrightarrow \mathrm{SO}_{2}(\mathrm{g})+\mathrm{H}_{2} \mathrm{O}(\mathrm{g})$
(d) $\mathrm{H}_{2} \mathrm{S}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \longrightarrow \mathrm{H}_{2} \mathrm{O}(\mathrm{g})+\mathrm{SO}_{2}(\mathrm{g})$
(not balanced)

Yongyao Zhou
Yongyao Zhou
Numerade Educator
05:03

Problem 6

Which substance in each of the following pairs would have the greater entropy? Explain.
(a) at $75^{\circ} \mathrm{C}$ and 1 atm: $1 \mathrm{mol} \mathrm{H}_{2} \mathrm{O}(1)$ or $1 \mathrm{mol} \mathrm{H}_{2} \mathrm{O}(\mathrm{g})$
(b) at $5^{\circ} \mathrm{C}$ and 1 atm: $50.0 \mathrm{g} \mathrm{Fe}(\mathrm{s})$ or $0.80 \mathrm{mol} \mathrm{Fe}(\mathrm{s})$
(c) 1 mol $\mathrm{Br}_{2}\left(1,1 \text { atm }, 8^{\circ} \mathrm{C}\right)$ or $1 \mathrm{mol} \mathrm{Br}_{2}(\mathrm{s}, 1 \mathrm{atm},$
$\left.-8^{\circ} \mathrm{C}\right)$
(d) $0.312 \mathrm{mol} \mathrm{SO}_{2}\left(\mathrm{g}, 0.110 \mathrm{atm}, 32.5^{\circ} \mathrm{C}\right)$ or $0.284 \mathrm{mol}$
$\mathrm{O}_{2}\left(\mathrm{g}, 15.0 \mathrm{atm}, 22.3^{\circ} \mathrm{C}\right)$

Yongyao Zhou
Yongyao Zhou
Numerade Educator
05:12

Problem 7

For each of the following reactions, indicate whether
$\Delta S$ for the reaction should be positive or negative. If it is not possible to determine the sign of $\Delta S$ from the information given, indicate why.
(a) $\mathrm{CaO}(\mathrm{s})+\mathrm{H}_{2} \mathrm{O}(\mathrm{l}) \longrightarrow \mathrm{Ca}(\mathrm{OH})_{2}(\mathrm{s})$
(b) $2 \mathrm{HgO}(\mathrm{s}) \longrightarrow 2 \mathrm{Hg}(1)+\mathrm{O}_{2}(\mathrm{g})$
(c) $2 \mathrm{NaCl}(1) \longrightarrow 2 \mathrm{Na}(1)+\mathrm{Cl}_{2}(\mathrm{g})$
(d) $\mathrm{Fe}_{2} \mathrm{O}_{3}(\mathrm{s})+3 \mathrm{CO}(\mathrm{g}) \longrightarrow 2 \mathrm{Fe}(\mathrm{s})+3 \mathrm{CO}_{2}(\mathrm{g})$
(e) $\operatorname{Si}\left(\text { s) }+2 \mathrm{Cl}_{2}(\mathrm{g}) \longrightarrow \mathrm{SiCl}_{4}(\mathrm{g})\right.$

Yongyao Zhou
Yongyao Zhou
Numerade Educator
01:57

Problem 8

By analogy to $\Delta H_{\mathrm{f}}^{\circ}$ and $\Delta G_{\mathrm{f}}^{\circ}$ how would you define entropy of formation? Which would have the largest entropy of formation: $\mathrm{CH}_{4}(\mathrm{g}), \mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{OH}(1), \mathrm{or}$
$\mathrm{CS}_{2}(1) ?$ First make a qualitative prediction; then test your prediction with data from Appendix D.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
03:14

Problem 9

In Example $19-2,$ we dealt with $\Delta H_{\text {vap }}^{\circ}$ and $\Delta S_{\text {vap }}^{\circ}$ for water at $100^{\circ} \mathrm{C}$
(a) Use data from Appendix D to determine values for these two quantities at $25^{\circ} \mathrm{C}$.
(b) From your knowledge of the structure of liquid water, explain the differences in $\Delta H_{\text {vap }}^{\circ}$ values and in $\Delta S_{\text {vap }}^{\circ}$ values between $25^{\circ} \mathrm{C}$ and $100^{\circ} \mathrm{C}$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
04:00

Problem 10

Pentane is one of the most volatile of the hydrocarbons in gasoline. At $298.15 \mathrm{K}$, the following enthalpies of formation are given for pentane: $\Delta H_{\mathrm{f}}^{\circ} \mathrm{C}_{5} \mathrm{H}_{12}(1)=$
$-173.5 \mathrm{kJ} \mathrm{mol}^{-1} ; \Delta H_{\mathrm{f}}^{9}\left[\mathrm{C}_{5} \mathrm{H}_{12}(\mathrm{g})\right]=-146.9 \mathrm{kJ} \mathrm{mol}^{-1}$
(a) Estimate the normal boiling point of pentane.
(b) Estimate $\Delta G^{\circ}$ for the vaporization of pentane
at $298 \mathrm{K}$
(c) Comment on the significance of the sign of $\Delta G^{\circ}$
at $298 \mathrm{K}$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
01:41

Problem 11

Which of the following substances would obey Trouton's rule most closely: HF, $\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{CH}_{3}$ (toluene), or $\mathrm{CH}_{3} \mathrm{OH}$ (methanol)? Explain your reasoning.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
01:12

Problem 12

Estimate the normal boiling point of bromine, $\mathrm{Br}_{2},$ in the following way: Determine $\Delta H_{\text {vap for }}^{\circ} \mathrm{Br}_{2}$ from data in Appendix D. Assume that $\Delta H_{\text {vap }}^{\circ}$ remains constant and that Trouton's rule is obeyed.

Rashmi Sinha
Rashmi Sinha
Numerade Educator
03:50

Problem 13

In what temperature range can the following equilibrium be established? Explain.
$$\mathrm{H}_{2} \mathrm{O}(1,0.50 \mathrm{atm}) \rightleftharpoons \mathrm{H}_{2} \mathrm{O}(\mathrm{g}, 0.50 \mathrm{atm})$$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
01:50

Problem 14

Refer to Figures $12-28$ and $19-9 .$ Which has the lowest Gibbs energy at 1 atm and $-60^{\circ} \mathrm{C}$ : solid, liquid, or gaseous carbon dioxide? Explain.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
03:02

Problem 15

Which of the following changes in a thermodynamic property would you expect to find for the reaction $\mathrm{Br}_{2}(\mathrm{g}) \longrightarrow 2 \mathrm{Br}(\mathrm{g})$ at all temperatures: $(\mathrm{a}) \Delta H<0$
(b) $\Delta S>0 ;$ (c) $\Delta G<0 ;$ (d) $\Delta S<0 ?$ Explain.

Jesse Leeder
Jesse Leeder
Numerade Educator
02:10

Problem 16

If a reaction can be carried out only by electrolysis, which of the following changes in a thermodynamic property must apply: (a) $\Delta H>0 ;$ (b) $\Delta S>0$
(c) $\Delta G=\Delta H ;$ (d) $\Delta G>0 ?$ Explain.

Yongyao Zhou
Yongyao Zhou
Numerade Educator
02:10

Problem 17

Indicate which of the four cases in Table 19.1 applies to each of the following reactions. If you are unable to decide from only the information given, state why.
(a) $\mathrm{PCl}_{3}(\mathrm{g})+\mathrm{Cl}_{2}(\mathrm{g}) \longrightarrow \mathrm{PCl}_{5}(\mathrm{g}) \Delta H^{\circ}=-87.9 \mathrm{kJ}$
(b) $\mathrm{CO}_{2}(\mathrm{g})+\mathrm{H}_{2}(\mathrm{g}) \longrightarrow \mathrm{CO}(\mathrm{g})+\mathrm{H}_{2} \mathrm{O}(\mathrm{g})$
$\Delta H^{\circ}=+41.2 \mathrm{kJ}$
(c) $\mathrm{NH}_{4} \mathrm{CO}_{2} \mathrm{NH}_{2}(\mathrm{s}) \longrightarrow 2 \mathrm{NH}_{3}(\mathrm{g})+\mathrm{CO}_{2}(\mathrm{g})$
$\Delta H^{\circ}=+159.2 \mathrm{kJ}$

Yongyao Zhou
Yongyao Zhou
Numerade Educator
07:33

Problem 18

Indicate which of the four cases in Table 19.1 applies to each of the following reactions. If you are unable to decide from only the information given, state why.
(a) $\mathrm{H}_{2} \mathrm{O}(\mathrm{g})+\frac{1}{2} \mathrm{O}_{2}(\mathrm{g}) \longrightarrow \mathrm{H}_{2} \mathrm{O}_{2}(\mathrm{g})$
$\Delta H^{\circ}=+105.5 \mathrm{kJ}$
(b) $\mathrm{C}_{6} \mathrm{H}_{6}(1)+\frac{15}{2} \mathrm{O}_{2}(\mathrm{g}) \longrightarrow 6 \mathrm{CO}_{2}(\mathrm{g})+3 \mathrm{H}_{2} \mathrm{O}(\mathrm{g})$
$\Delta H^{\circ}=-3135 \mathrm{kJ}$
(c) $\mathrm{NO}(\mathrm{g})+\frac{1}{2} \mathrm{Cl}_{2}(\mathrm{g}) \longrightarrow \mathrm{NOCl}(\mathrm{g})$
$\Delta H^{\circ}=-38.54 \mathrm{kJ}$

Yongyao Zhou
Yongyao Zhou
Numerade Educator
01:53

Problem 19

For the mixing of ideal gases (see Figure $19-2$ ), explain whether a positive, negative, or zero value is expected for $\Delta H, \Delta S,$ and $\Delta G$

Alexander Clippinger
Alexander Clippinger
Numerade Educator
01:22

Problem 20

What values of $\Delta H, \Delta S,$ and $\Delta G$ would you expect for the formation of an ideal solution of liquid components? (Is each value positive, negative, or zero?)

Alexander Clippinger
Alexander Clippinger
Numerade Educator
04:21

Problem 21

Explain why (a) some exothermic reactions do not occur spontaneously, and (b) some reactions in which the entropy of the system increases do not occur spontaneously.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
03:22

Problem 22

Explain why you would expect a reaction of the type $\mathrm{AB}(\mathrm{g}) \longrightarrow \mathrm{A}(\mathrm{g})+\mathrm{B}(\mathrm{g})$ always to be spontaneous
at high rather than at low temperatures.

Jesse Leeder
Jesse Leeder
Numerade Educator
07:36

Problem 23

From the data given in the following table, determine
$\Delta S^{\circ} \quad$ for the reaction $\quad \mathrm{NH}_{3}(\mathrm{g})+\mathrm{HCl}(\mathrm{g}) \longrightarrow$
$\mathrm{NH}_{4} \mathrm{Cl}(\mathrm{s}) .$ All data are at $298 \mathrm{K}$ $$\begin{array}{lcc}
\hline & \Delta H_{f}^{\circ}, \mathrm{kJ} \mathrm{mol}^{-1} & \Delta G_{f,}^{\circ} \mathrm{kJ} \mathrm{mol}^{-1} \\
\hline \mathrm{NH}_{3}(\mathrm{g}) & -46.11 & -16.48 \\
\mathrm{HCl}(\mathrm{g}) & -92.31 & -95.30 \\
\mathrm{NH}_{4} \mathrm{Cl}(\mathrm{s}) & -314.4 & -202.9 \\
\hline
\end{array}$$

Yongyao Zhou
Yongyao Zhou
Numerade Educator
06:48

Problem 24

Use data from Appendix D to determine values of $\Delta G^{\circ}$ for the following reactions at $25^{\circ} \mathrm{C}$
(a) $\mathrm{C}_{2} \mathrm{H}_{2}(\mathrm{g})+2 \mathrm{H}_{2}(\mathrm{g}) \longrightarrow \mathrm{C}_{2} \mathrm{H}_{6}(\mathrm{g})$
(b) $2 \mathrm{SO}_{3}(\mathrm{g}) \longrightarrow 2 \mathrm{SO}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g})$
(c) $\mathrm{Fe}_{3} \mathrm{O}_{4}(\mathrm{s})+4 \mathrm{H}_{2}(\mathrm{g}) \longrightarrow 3 \mathrm{Fe}(\mathrm{s})+4 \mathrm{H}_{2} \mathrm{O}(\mathrm{g})$
(d) $2 \mathrm{Al}(\mathrm{s})+6 \mathrm{H}^{+}(\mathrm{aq}) \longrightarrow 2 \mathrm{Al}^{3+}(\mathrm{aq})+3 \mathrm{H}_{2}(\mathrm{g})$

Yongyao Zhou
Yongyao Zhou
Numerade Educator
04:09

Problem 25

At $298 \mathrm{K},$ for the reaction $2 \mathrm{PCl}_{3}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \stackrel{\text { Lest }}{\longrightarrow}$
$2 \mathrm{POCl}_{3}(1), \Delta H^{\circ}=-620.2 \mathrm{kJ}$ and the standard molar
entropies are $\mathrm{PCl}_{3}(\mathrm{g}), 311.8 \mathrm{JK}^{-1} ; \mathrm{O}_{2}(\mathrm{g}), 205.1 \mathrm{JK}^{-1}$
and $\mathrm{POCl}_{3}(1), 222.4 \mathrm{JK}^{-1} .$ Determine (a) $\Delta G^{\circ}$ at $298 \mathrm{K}$
and (b) whether the reaction proceeds spontaneously in the forward or the reverse direction when reactants and products are in their standard states.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
03:29

Problem 26

At $298 \mathrm{K},$ for the reaction $2 \mathrm{H}^{+}(\mathrm{aq})+2 \mathrm{Br}^{-}(\mathrm{aq})+$
$2 \mathrm{NO}_{2}(\mathrm{g}) \longrightarrow \mathrm{Br}_{2}(1)+2 \mathrm{HNO}_{2}(\mathrm{aq}), \Delta H^{\circ}=-61.6 \mathrm{kJ}$
and the standard molar entropies are $\mathrm{H}^{+}(\mathrm{aq}), 0 \mathrm{JK}^{-1}$ $\mathrm{Br}^{-}(\mathrm{aq}), 82.4 \mathrm{JK}^{-1} ; \mathrm{NO}_{2}(\mathrm{g}), 240.1 \mathrm{JK}^{-1} ; \mathrm{Br}_{2}(1), 152.2$
$\mathrm{J} \mathrm{K}^{-1} ; \mathrm{HNO}_{2}(\mathrm{aq}), 135.6 \mathrm{JK}^{-1} .$ Determine (a) $\Delta G^{\circ}$ at
298 K and (b) whether the reaction proceeds spontaneously in the forward or the reverse direction when reactants and products are in their standard states.

Jesse Leeder
Jesse Leeder
Numerade Educator
08:01

Problem 27

The following standard Gibbs energy changes are given for $25^{\circ} \mathrm{C}$
(1) $\mathrm{N}_{2}(\mathrm{g})+3 \mathrm{H}_{2}(\mathrm{g}) \longrightarrow 2 \mathrm{NH}_{3}(\mathrm{g})$
$\Delta G^{\circ}=-33.0 \mathrm{kJ}$
(2) $4 \mathrm{NH}_{3}(\mathrm{g})+5 \mathrm{O}_{2}(\mathrm{g}) \longrightarrow 4 \mathrm{NO}(\mathrm{g})+6 \mathrm{H}_{2} \mathrm{O}(1)$
$\Delta G^{\circ}=-1010.5 \mathrm{kJ}$
(3) $\mathrm{N}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \longrightarrow 2 \mathrm{NO}(\mathrm{g})$
$\Delta G^{\circ}=+173.1 \mathrm{kJ}$
(4) $\mathrm{N}_{2}(\mathrm{g})+2 \mathrm{O}_{2}(\mathrm{g}) \longrightarrow 2 \mathrm{NO}_{2}(\mathrm{g})$
$\Delta G^{\circ}=+102.6 \mathrm{kJ}$
(5) $2 \mathrm{N}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \longrightarrow 2 \mathrm{N}_{2} \mathrm{O}(\mathrm{g})$
$\Delta G^{\circ}=+208.4 \mathrm{kJ}$
Combine the preceding equations, as necessary, to obtain $\Delta G^{\circ}$ values for each of the following reactions.
(a) $\mathrm{N}_{2} \mathrm{O}(\mathrm{g})+\frac{3}{2} \mathrm{O}_{2}(\mathrm{g}) \longrightarrow 2 \mathrm{NO}_{2}(\mathrm{g}) \quad \Delta G^{\circ}=?$
(b) $2 \mathrm{H}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \longrightarrow 2 \mathrm{H}_{2} \mathrm{O}(1) \quad \Delta G^{\circ}=?$
(c) $2 \mathrm{NH}_{3}(\mathrm{g})+2 \mathrm{O}_{2}(\mathrm{g}) \longrightarrow \mathrm{N}_{2} \mathrm{O}(\mathrm{g})+3 \mathrm{H}_{2} \mathrm{O}(1)$
$\Delta G^{\circ}=?$
Of reactions (a), (b), and (c), which would tend to go to completion at $25^{\circ} \mathrm{C}$, and which would reach an equilibrium condition with significant amounts of all reactants and products present?

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
03:37

Problem 28

The following standard Gibbs energy changes are given for $25^{\circ} \mathrm{C}$
(1) $\mathrm{SO}_{2}(\mathrm{g})+3 \mathrm{CO}(\mathrm{g}) \longrightarrow \operatorname{COS}(\mathrm{g})+2 \mathrm{CO}_{2}(\mathrm{g})$
$\Delta G^{\circ}=-246.4 \mathrm{kJ}$
(2) $\mathrm{CS}_{2}(\mathrm{g})+\mathrm{H}_{2} \mathrm{O}(\mathrm{g}) \longrightarrow \operatorname{COS}(\mathrm{g})+\mathrm{H}_{2} \mathrm{S}(\mathrm{g})$
$\Delta G^{\circ}=-41.5 \mathrm{kJ}$
(3) $\mathrm{CO}(\mathrm{g})+\mathrm{H}_{2} \mathrm{S}(\mathrm{g}) \longrightarrow \operatorname{COS}(\mathrm{g})+\mathrm{H}_{2}(\mathrm{g})$
$\Delta G^{\circ}=+1.4 \mathrm{kJ}$
(4) $\mathrm{CO}(\mathrm{g})+\mathrm{H}_{2} \mathrm{O}(\mathrm{g}) \longrightarrow \mathrm{CO}_{2}(\mathrm{g})+\mathrm{H}_{2}(\mathrm{g})$
$\Delta G^{\circ}=-28.6 \mathrm{kJ}$
Combine the preceding equations, as necessary, to obtain $\Delta G^{\circ}$ values for the following reactions.
(a) $\operatorname{COS}(\mathrm{g})+2 \mathrm{H}_{2} \mathrm{O}(\mathrm{g}) \longrightarrow$
$\begin{aligned} \mathrm{SO}_{2}(\mathrm{g})+\mathrm{CO}(\mathrm{g})+2 \mathrm{H}_{2}(\mathrm{g}) & \Delta G^{\circ}=? \end{aligned}$
(b) $\cos (g)+3 \mathrm{H}_{2} \mathrm{O}(\mathrm{g}) \longrightarrow$
$\mathrm{SO}_{2}(\mathrm{g})+\mathrm{CO}_{2}(\mathrm{g})+3 \mathrm{H}_{2}(\mathrm{g}) \quad \Delta G^{\circ}=?$
$\left.+\quad \mathrm{H}_{\mathrm{O}} \mathrm{C}(\mathrm{d})=\mathrm{CO}_{-}^{\circ} \mathrm{G}\right)+\mathrm{H}_{-}^{-} \mathrm{S}(\mathrm{q})$
(c) $\cos (\mathrm{g})+\mathrm{H}_{2} \mathrm{O}(\mathrm{g}) \longrightarrow \mathrm{CO}_{2}(\mathrm{g})+\mathrm{H}_{2} \mathrm{S}(\mathrm{g})$
$\Delta G^{\circ}=?$
Of reactions (a), (b), and (c), which is spontaneous in the forward direction when reactants and products are present in their standard states?

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
03:26

Problem 29

Write an equation for the combustion of one mole of benzene, $\mathrm{C}_{6} \mathrm{H}_{6}(1),$ and use data from Appendix $\mathrm{D}$ to determine $\Delta G^{\circ}$ at $298 \mathrm{K}$ if the products of the combustion are (a) $\mathrm{CO}_{2}(\mathrm{g})$ and $\mathrm{H}_{2} \mathrm{O}(1),$ and $(\mathrm{b}) \mathrm{CO}_{2}(\mathrm{g})$ and
$\mathrm{H}_{2} \mathrm{O}(\mathrm{g}) .$ Describe how you might determine the difference between the values obtained in (a) and (b) without having either to write the combustion equation or to determine $\Delta G^{\circ}$ values for the combustion reactions.

Jesse Leeder
Jesse Leeder
Numerade Educator
04:50

Problem 30

Use molar entropies from Appendix D, together with the following data, to estimate the bond-dissociation energy of the $\mathrm{F}_{2}$ molecule.
$$\mathrm{F}_{2}(\mathrm{g}) \longrightarrow 2 \mathrm{F}(\mathrm{g}) \Delta G^{\circ}=123.9 \mathrm{kJ}$$
Compare your result with the value listed in Table 10.3 .

Yongyao Zhou
Yongyao Zhou
Numerade Educator
05:23

Problem 31

Assess the feasibility of the reaction
$$\mathrm{N}_{2} \mathrm{H}_{4}(\mathrm{g})+2 \mathrm{OF}_{2}(\mathrm{g}) \longrightarrow \mathrm{N}_{2} \mathrm{F}_{4}(\mathrm{g})+2 \mathrm{H}_{2} \mathrm{O}(\mathrm{g})$$
by determining each of the following quantities for this reaction at $25^{\circ} \mathrm{C}$
(a) $\Delta S^{\circ}$ (The standard molar entropy of $\mathrm{N}_{2} \mathrm{F}_{4}(\mathrm{g})$ is $\left.301.2 \mathrm{JK}^{-1} .\right)$
(b) $\Delta H^{\circ}$ (Use data from Table 10.3 and $\mathrm{F}-\mathrm{O}$ and $\mathrm{N}-\mathrm{F}$ bond energies of 222 and $301 \mathrm{kJ} \mathrm{mol}^{-1}$ respectively.)
(c) $\Delta G^{\circ}$ Is the reaction feasible? If so, is it favored at high or low temperatures?

Rashmi Sinha
Rashmi Sinha
Numerade Educator
04:16

Problem 32

Solid ammonium nitrate can decompose to dinitrogen oxide gas and liquid water. What is $\Delta G^{\circ}$ at $298 \mathrm{K} ?$ Is the decomposition reaction favored at temperatures above or below 298 K?

Narayan Hari
Narayan Hari
Numerade Educator
02:55

Problem 33

For one of the following reactions, $K_{c} K_{p}=K .$ Identify that reaction. For the other two reactions, what is the relationship between $K_{c}, \bar{K}_{\mathrm{p}},$ and $K ?$ Explain.
(a) $2 \mathrm{SO}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{SO}_{3}(\mathrm{g})$
(b) $\mathrm{HI}(\mathrm{g}) \rightleftharpoons \frac{1}{2} \mathrm{H}_{2}(\mathrm{g})+\frac{1}{2} \mathrm{I}_{2}(\mathrm{g})$
(c) $\mathrm{NH}_{4} \mathrm{HCO}_{3}(\mathrm{s}) \rightleftharpoons \mathrm{NH}_{3}(\mathrm{g})+\mathrm{CO}_{2}(\mathrm{g})+\mathrm{H}_{2} \mathrm{O}(1)$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
03:30

Problem 34

$\mathrm{H}_{2}(\mathrm{g})$ can be prepared by passing steam over hot iron: $3 \mathrm{Fe}(\mathrm{s})+4 \mathrm{H}_{2} \mathrm{O}(\mathrm{g}) \rightleftharpoons \mathrm{Fe}_{3} \mathrm{O}_{4}(\mathrm{s})+4 \mathrm{H}_{2}(\mathrm{g})$
(a) Write an expression for the thermodynamic equilibrium constant for this reaction.
(b) Explain why the partial pressure of $\mathrm{H}_{2}(\mathrm{g})$ is independent of the amounts of $\mathrm{Fe}(\mathrm{s})$ and $\mathrm{Fe}_{3} \mathrm{O}_{4}(\mathrm{s})$ present.
(c) Can we conclude that the production of $\mathrm{H}_{2}(\mathrm{g})$ from $\mathrm{H}_{2} \mathrm{O}(\mathrm{g})$ could be accomplished regardless of the proportions of $\mathrm{Fe}(\mathrm{s})$ and $\mathrm{Fe}_{3} \mathrm{O}_{4}(\mathrm{s})$ present? Explain.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
05:02

Problem 35

In the synthesis of gaseous methanol from carbon monoxide gas and hydrogen gas, the following equilibrium concentrations were determined at $483 \mathrm{K}:[\mathrm{CO}(\mathrm{g})]=0.0911 \mathrm{M}, \quad\left[\mathrm{H}_{2} \mathrm{O}(\mathrm{g})\right]=0.0822 \mathrm{M}$
and $\left[\mathrm{CH}_{3} \mathrm{OH}(\mathrm{g})\right]=0.00892 \mathrm{M} .$ Calculate the equilibrium constant and Gibbs energy for this reaction.

Yongyao Zhou
Yongyao Zhou
Numerade Educator
02:22

Problem 36

Calculate the equilibrium constant and Gibbs energy for the reaction $\mathrm{CO}(\mathrm{g})+2 \mathrm{H}_{2}(\mathrm{g}) \longrightarrow \mathrm{CH}_{3} \mathrm{OH}(\mathrm{g})$
at $483 \mathrm{K}$ by using the data tables from Appendix D. Are the values determined here different from or the same as those in exercise $35 ?$ Explain.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
02:18

Problem 37

Use data from Appendix D to determine $K_{\mathrm{p}}$ at $298 \mathrm{K}$ for the reaction $\mathrm{N}_{2} \mathrm{O}(\mathrm{g})+\frac{1}{2} \mathrm{O}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{NO}(\mathrm{g})$.

Kristen Justice
Kristen Justice
Numerade Educator
02:40

Problem 38

Use data from Appendix D to establish for the reac$\operatorname{tion} 2 \mathrm{N}_{2} \mathrm{O}_{4}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{N}_{2} \mathrm{O}_{5}(\mathrm{g})$
(a) $\Delta G^{\circ}$ at $298 \mathrm{K}$ for the reaction as written;
(b) $K_{p}$ at $298 \mathrm{K}$

Alexander Clippinger
Alexander Clippinger
Numerade Educator
07:35

Problem 39

Use data from Appendix D to determine values at $298 \mathrm{K}$ of $\Delta G^{\circ}$ and $K$ for the following reactions. (Note: The equations are not balanced.)
(a) $\mathrm{HCl}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \rightleftharpoons \mathrm{H}_{2} \mathrm{O}(\mathrm{g})+\mathrm{Cl}_{2}(\mathrm{g})$
(b) $\mathrm{Fe}_{2} \mathrm{O}_{3}(\mathrm{s})+\mathrm{H}_{2}(\mathrm{g}) \rightleftharpoons \mathrm{Fe}_{3} \mathrm{O}_{4}(\mathrm{s})+\mathrm{H}_{2} \mathrm{O}(\mathrm{g})$
(c) $\mathrm{Ag}^{+}(\mathrm{aq})+\mathrm{SO}_{4}^{2-}(\mathrm{aq}) \rightleftharpoons \mathrm{Ag}_{2} \mathrm{SO}_{4}(\mathrm{s})$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
02:03

Problem 40

In Example $19-1,$ we were unable to conclude by inspection whether $\Delta S^{\circ}$ for the reaction $\mathrm{CO}(\mathrm{g})+$ $\mathrm{H}_{2} \mathrm{O}(\mathrm{g}) \longrightarrow \mathrm{CO}_{2}(\mathrm{g})+\mathrm{H}_{2}(\mathrm{g})$ should be positive or negative. Use data from Appendix D to obtain $\Delta S^{\circ}$ at $298 \mathrm{K}$.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
02:37

Problem 41

Use thermodynamic data at $298 \mathrm{K}$ to decide in which direction the reaction
$$2 \mathrm{SO}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{SO}_{3}(\mathrm{g})$$
is spontaneous when the partial pressures of $\mathrm{SO}_{2}, \mathrm{O}_{2},$ and $\mathrm{SO}_{3}$ are $1.0 \times 10^{-4}, 0.20,$ and $0.10 \mathrm{atm}$
respectively.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
04:34

Problem 42

Use thermodynamic data at $298 \mathrm{K}$ to decide in which direction the reaction
$$\mathrm{H}_{2}(\mathrm{g})+\mathrm{Cl}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{HCl}(\mathrm{g})$$
is spontaneous when the partial pressures of $\mathrm{H}_{2}, \mathrm{Cl}_{2}$ and HCl are all 0.5 atm.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
03:16

Problem 43

The standard Gibbs energy change for the reaction
$\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{H}(\mathrm{aq})+\mathrm{H}_{2} \mathrm{O}(\mathrm{l}) \rightleftharpoons$$$
\mathrm{CH}_{3} \mathrm{CO}_{2}^{-}(\mathrm{aq})+\mathrm{H}_{3} \mathrm{O}^{+}(\mathrm{aq})$$is $27.07 \mathrm{kJmol}^{-1}$ at 298 K. Use this thermodynamic quantity to decide in which direction the reaction is spontaneous when the concentrations of $\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{H}(\mathrm{aq}), \mathrm{CH}_{3} \mathrm{CO}_{2}^{-}(\mathrm{aq}),$ and $\mathrm{H}_{3} \mathrm{O}^{+}(\mathrm{aq})$ are $0.10 \mathrm{M}, 1.0 \times 10^{-3} \mathrm{M},$ and $1.0 \times 10^{-3} \mathrm{M},$ respectively.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
02:57

Problem 44

The standard Gibbs energy change for the reaction
$$\mathrm{NH}_{3}(\mathrm{aq})+\mathrm{H}_{2} \mathrm{O}(1) \rightleftharpoons \mathrm{NH}_{4}^{+}(\mathrm{aq})+\mathrm{OH}^{-}(\mathrm{aq})$$
is $29.05 \mathrm{kJ} \mathrm{mol}^{-1}$ at $298 \mathrm{K}$. Use this thermodynamic quantity to decide in which direction the reaction is spontaneous when the concentrations of $\mathrm{NH}_{3}(\mathrm{aq})$ $\mathrm{NH}_{4}^{+}(\mathrm{aq}),$ and $\mathrm{OH}^{-}(\mathrm{aq})$ are $0.10 \mathrm{M}, 1.0 \times 10^{-3} \mathrm{M}$
and $1.0 \times 10^{-3} \mathrm{M},$ respectively.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
01:12

Problem 45

For the reaction $2 \mathrm{NO}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \longrightarrow 2 \mathrm{NO}_{2}(\mathrm{g})$
all but one of the following equations is correct. Which is incorrect, and why? (a) $K=K_{\mathrm{p}} ;$ (b) $\Delta S^{\circ}=$ $\left(\Delta G^{\circ}-\Delta H^{\circ}\right) / T ;\left(\text { c) } K_{\mathrm{p}}=e^{-\Delta G^{\circ} / R T} ;(\mathrm{d}) \Delta G=\Delta G^{\circ}+\right.$
$R T \ln Q$.

Ck
Chandra Kala
Numerade Educator
01:45

Problem 46

Why is $\Delta G^{\circ}$ such an important property of a chemical reaction, even though the reaction is generally carried out under nonstandard conditions?

Alexander Clippinger
Alexander Clippinger
Numerade Educator
04:36

Problem 47

At $1000 \mathrm{K},$ an equilibrium mixture in the reaction $\mathrm{CO}_{2}(\mathrm{g})+\mathrm{H}_{2}(\mathrm{g}) \rightleftharpoons \mathrm{CO}(\mathrm{g})+\mathrm{H}_{2} \mathrm{O}(\mathrm{g}) \quad$ contains
$0.276 \mathrm{mol} \quad \mathrm{H}_{2}, 0.276 \mathrm{mol} \mathrm{CO}_{2}, \quad 0.224 \mathrm{mol} \mathrm{CO}, \quad$ and
$0.224 \mathrm{mol} \mathrm{H}_{2} \mathrm{O}$
(a) What is $K_{\mathrm{p}}$ at $1000 \mathrm{K} ?$
(b) Calculate $\Delta G^{\circ}$ at $1000 \mathrm{K}$.
(c) In which direction would a spontaneous reaction occur if the following were brought together at 1000
K: $0.0750 \mathrm{mol} \mathrm{CO}_{2}, 0.095 \mathrm{mol} \mathrm{H}_{2}, 0.0340 \mathrm{mol} \mathrm{CO},$ and
$0.0650 \mathrm{mol} \mathrm{H}_{2} \mathrm{O} ?$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
01:07

Problem 48

For the reaction $2 \mathrm{SO}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{SO}_{3}(\mathrm{g})$
$K_{\mathrm{c}}=2.8 \times 10^{2}$ at $1000 \mathrm{K}$
(a) What is $\Delta G^{\circ}$ at $1000 \mathrm{K} ?\left[\text { Hint: What is } \mathrm{K}_{\mathrm{p}} ?\right]$
(b) If $0.40 \mathrm{mol} \mathrm{SO}_{2}, 0.18 \mathrm{mol} \mathrm{O}_{2},$ and $0.72 \mathrm{mol} \mathrm{SO}_{3}$ are
mixed in a 2.50 L flask at $1000 \mathrm{K}$, in what direction will a net reaction occur?

Ronald Prasad
Ronald Prasad
Numerade Educator
02:21

Problem 49

For the following equilibrium reactions, calculate $\Delta G^{\circ}$ at the indicated temperature. [Hint: How is each equilibrium constant related to a thermodynamic equilibrium constant, $K ?]$
(a) $\mathrm{H}_{2}(\mathrm{g})+\mathrm{I}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{HI}(\mathrm{g}) \quad K_{\mathrm{c}}=50.2$ at $445^{\circ} \mathrm{C}$
(b) $\mathrm{N}_{2} \mathrm{O}(\mathrm{g})+\frac{1}{2} \mathrm{O}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{NO}(\mathrm{g})$
$K_{c}=1.7 \times 10^{-13} \mathrm{at} 25^{\circ} \mathrm{C}$
(c) $\mathrm{N}_{2} \mathrm{O}_{4}(\mathrm{g}) \rightleftharpoons 2 \mathrm{NO}_{2}(\mathrm{g})$
$K_{c}=4.61 \times 10^{-3}$ at $25^{\circ} \mathrm{C}$
(d) $2 \mathrm{Fe}^{3+}(\mathrm{aq})+\mathrm{Hg}_{2}^{2+}(\mathrm{aq}) \rightleftharpoons$
$2 \mathrm{Fe}^{2+}(\mathrm{aq})+2 \mathrm{Hg}^{2+}(\mathrm{aq})$
$K_{\mathrm{c}}=9.14 \times 10^{-6} \mathrm{at} 25^{\circ} \mathrm{C}$

Alexander Clippinger
Alexander Clippinger
Numerade Educator
04:04

Problem 50

Two equations can be written for the dissolution of $\mathrm{Mg}(\mathrm{OH})_{2}(\mathrm{s})$ in acidic solution. $$\begin{aligned}
\mathrm{Mg}(\mathrm{OH})_{2}(\mathrm{s})+2 \mathrm{H}^{+}(\mathrm{aq}) \rightleftharpoons & \mathrm{Mg}^{2+}(\mathrm{aq})+2 \mathrm{H}_{2} \mathrm{O}(1) \\
& \Delta G^{\circ}=-95.5 \mathrm{kJ} \mathrm{mol}^{-1} \\
(c) Will the solubilities of $\mathrm{Mg}(\mathrm{OH})_{2}(\mathrm{s})$ in a buffer solution at $\mathrm{pH}=8.5$ depend on which of the two equations is used as the basis of the calculation? Explain.
\frac{1}{2} \mathrm{Mg}(\mathrm{OH})_{2}(\mathrm{s})+\mathrm{H}^{+}(\mathrm{aq}) \rightleftharpoons & \frac{1}{2} \mathrm{Mg}^{2+}(\mathrm{aq})+\mathrm{H}_{2} \mathrm{O}(1) \\
& \Delta G^{\circ}=-47.8 \mathrm{kJ} \mathrm{mol}^{-1}
\end{aligned}$$
(a) Explain why these two equations have different
$\Delta G^{\circ}$ values.
(b) Will $K$ for these two equations be the same or different? Explain.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
04:09

Problem 51

At $298 \mathrm{K}, \Delta G_{\mathrm{f}}^{\mathrm{p}}[\mathrm{CO}(\mathrm{g})]=-137.2 \mathrm{kJ} / \mathrm{mol}$ and $K_{\mathrm{p}}=$
$6.5 \times 10^{11}$ for the reaction $\mathrm{CO}(\mathrm{g})+\mathrm{Cl}_{2}(\mathrm{g}) \rightleftharpoons$
$\mathrm{COCl}_{2}(\mathrm{g}) . \quad$ Use these data to determine $\Delta G_{f}\left[\mathrm{COCl}_{2}(\mathrm{g})\right],$ and compare your result with the value in Appendix D.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
03:33

Problem 52

Use thermodynamic data from Appendix D to calculate values of $K_{\mathrm{sp}}$ for the following sparingly soluble solutes: (a) $\operatorname{AgBr} ;$ (b) $\operatorname{CaSO}_{4} ;$ (c) $\operatorname{Fe}(\text { OH })_{3}$. [Hint: Begin by writing solubility equilibrium expressions.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
04:54

Problem 53

To establish the law of conservation of mass, Lavoisier carefully studied the decomposition of mercury(II) oxide:
$$\mathrm{HgO}(\mathrm{s}) \longrightarrow \mathrm{Hg}(1)+\frac{1}{2} \mathrm{O}_{2}(\mathrm{g})$$
At $25^{\circ} \mathrm{C}, \Delta H^{\circ}=+90.83 \mathrm{kJ}$ and $\Delta G^{\circ}=+58.54 \mathrm{kJ}$
(a) Show that the partial pressure of $\mathrm{O}_{2}(\mathrm{g})$ in equilibrium with $\mathrm{HgO}(\mathrm{s})$ and $\mathrm{Hg}(\mathrm{l})$ at $25^{\circ} \mathrm{C}$ is extremely low.
(b) What conditions do you suppose Lavoisier used to obtain significant quantities of oxygen?

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
09:08

Problem 54

Currently, $\mathrm{CO}_{2}$ is being studied as a source of carbon atoms for synthesizing organic compounds. One possible reaction involves the conversion of $\mathrm{CO}_{2}$ to methanol, $\mathrm{CH}_{3} \mathrm{OH}$
$$\mathrm{CO}_{2}(\mathrm{g})+3 \mathrm{H}_{2}(\mathrm{g}) \longrightarrow \mathrm{CH}_{3} \mathrm{OH}(\mathrm{g})+\mathrm{H}_{2} \mathrm{O}(\mathrm{g})$$
With the aid of data from Appendix D, determine
(a) if this reaction proceeds to any significant extent at $25^{\circ} \mathrm{C}$
(b) if the production of $\mathrm{CH}_{3} \mathrm{OH}(\mathrm{g})$ is favored by raising or lowering the temperature from $25^{\circ} \mathrm{C}$
(c) $K_{\mathrm{p}}$ for this reaction at $500 \mathrm{K}$
(d) the partial pressure of $\mathrm{CH}_{3} \mathrm{OH}(\mathrm{g})$ at equilibrium
if $\mathrm{CO}_{2}(\mathrm{g})$ and $\mathrm{H}_{2}(\mathrm{g}),$ each initially at a partial pressure of 1 atm, react at $500 \mathrm{K}$.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
04:08

Problem 55

Use data from Appendix D to establish at $298 \mathrm{K}$ for the reaction:
$2 \mathrm{NaHCO}_{3}(\mathrm{s}) \longrightarrow \mathrm{Na}_{2} \mathrm{CO}_{3}(\mathrm{s})+\mathrm{H}_{2} \mathrm{O}(1)+\mathrm{CO}_{2}(\mathrm{g})$
$\begin{array}{llll}\text { (a) } \Delta S^{\circ} ; & \text { (b) } \Delta H^{\circ} ; & \text { (c) } \Delta G^{\circ} ; & \text { (d) K. }\end{array}$

Alexander Clippinger
Alexander Clippinger
Numerade Educator
05:31

Problem 56

A possible reaction for converting methanol to ethanol is
$$\begin{aligned}
\mathrm{CO}(\mathrm{g})+2 \mathrm{H}_{2}(\mathrm{g})+\mathrm{CH}_{3} \mathrm{OH}(\mathrm{g}) & \longrightarrow \\
\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{OH}(\mathrm{g})+\mathrm{H}_{2} \mathrm{O}(\mathrm{g})
\end{aligned}$$
(a) Use data from Appendix D to calculate $\Delta H^{\circ}, \Delta S^{\circ}$ and $\Delta G^{\circ}$ for this reaction at $25^{\circ} \mathrm{C}$.
(b) Is this reaction thermodynamically favored at high or low temperatures? At high or low pressures? Explain.
(c) Estimate $K_{\mathrm{p}}$ for the reaction at $750 \mathrm{K}$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
01:50

Problem 57

What must be the temperature if the following reaction has $\Delta G^{\circ}=-45.5 \mathrm{kJ}, \Delta H^{\circ}=-24.8 \mathrm{kJ},$ and
$\Delta S^{\circ}=15.2 \mathrm{JK}^{-1} ?$
$$\mathrm{Fe}_{2} \mathrm{O}_{3}(\mathrm{s})+3 \mathrm{CO}(\mathrm{g}) \longrightarrow 2 \mathrm{Fe}(\mathrm{s})+3 \mathrm{CO}_{2}(\mathrm{g})$$

Jesse Leeder
Jesse Leeder
Numerade Educator
02:13

Problem 58

Estimate $K_{\mathrm{p}}$ at $100^{\circ} \mathrm{C}$ for the reaction $2 \mathrm{SO}_{2}(\mathrm{g})+$ $\mathrm{O}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{SO}_{3}(\mathrm{g}) .$ Use data from Table 19.3 and Figure $19-12$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
02:35

Problem 59

The synthesis of ammonia by the Haber process occurs by the reaction $\mathrm{N}_{2}(\mathrm{g})+3 \mathrm{H}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{NH}_{3}(\mathrm{g})$ at $400^{\circ} \mathrm{C} .$ Using data from Appendix D and assuming that $\Delta H^{\circ}$ and $\Delta S^{\circ}$ are essentially unchanged in the temperature interval from 25 to $400^{\circ} \mathrm{C}$, estimate $K_{\mathrm{p}}$ at
$400^{\circ} \mathrm{C}$

Alexander Clippinger
Alexander Clippinger
Numerade Educator
06:07

Problem 60

Use data from Appendix D to determine (a) $\Delta H^{\circ}, \Delta S^{\circ}$ and $\Delta G^{\circ}$ at $298 \mathrm{K}$ and $(\mathrm{b}) \mathrm{K}_{\mathrm{p}}$ at $875 \mathrm{K}$ for the water gas shift reaction, used commercially to produce $\mathrm{H}_{2}(\mathrm{g}):$ $\mathrm{CO}(\mathrm{g})+\mathrm{H}_{2} \mathrm{O}(\mathrm{g}) \rightleftharpoons \mathrm{CO}_{2}(\mathrm{g})+\mathrm{H}_{2}(\mathrm{g})$
[Hint: Assume that $\Delta H^{\circ}$ and $\Delta S^{\circ}$ are essentially unchanged in this temperature interval.]

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
03:10

Problem 61

In Example $19-10,$ we used the van't Hoff equation to determine the temperature at which $K_{\mathrm{p}}=1.0 \times 10^{6}$ for the reaction $2 \mathrm{SO}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{SO}_{3}(\mathrm{g}) .$ Obtain
another estimate of this temperature with data from Appendix D and equations (19.9) and (19.13). Compare your result with that obtained in Example $19-10$.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
02:13

Problem 62

The following equilibrium constants have been determined for the reaction $\mathrm{H}_{2}(\mathrm{g})+\mathrm{I}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{HI}(\mathrm{g})$
$K_{\mathrm{p}}=50.0$ at $448^{\circ} \mathrm{C}$ and 66.9 at $350^{\circ} \mathrm{C} .$ Use these data to estimate $\Delta H^{\circ}$ for the reaction.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
03:48

Problem 63

For the reaction $\mathrm{N}_{2} \mathrm{O}_{4}(\mathrm{g}) \rightleftharpoons 2 \mathrm{NO}_{2}(\mathrm{g})$
$\Delta H^{\circ}=+57.2 \mathrm{kJ} \mathrm{mol}^{-1}$ and $K_{\mathrm{p}}=0.113$ at $298 \mathrm{K}$
(a) What is $K_{\mathrm{p}}$ at $0^{\circ} \mathrm{C} ?$
(b) At what temperature will $K_{\mathrm{p}}=1.00 ?$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
04:41

Problem 64

Use data from Appendix D and the van't Hoff equation (19.15) to estimate a value of $K_{\mathrm{p}}$ at $100^{\circ} \mathrm{C}$ for the reaction $2 \mathrm{NO}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{NO}_{2}(\mathrm{g}) .$ [Hint: First
determine $\left.K_{\mathrm{p}} \text { at } 25^{\circ} \mathrm{C} . \text { What is } \Delta H^{\circ} \text { for the reaction? }\right]$

Carina Carlos
Carina Carlos
Numerade Educator
03:10

Problem 65

For the reaction
$$\begin{aligned}
\mathrm{CO}(\mathrm{g})+3 \mathrm{H}_{2}(\mathrm{g}) \rightleftharpoons \mathrm{CH}_{4}(\mathrm{g})+\mathrm{H}_{2} \mathrm{O}(\mathrm{g}), & \\
K_{\mathrm{p}} &=2.15 \times 10^{11} \mathrm{at} 200^{\circ} \mathrm{C} \\ determine $\Delta H^{\circ}$ by using the van't Hoff equation (19.15) and by using tabulated data in Appendix D. Compare the two results, and comment on how good the assumption is that $\Delta H^{\circ}$ is essentially independent of temperature in this case.
K_{\mathrm{p}} &=4.56 \times 10^{8} \mathrm{at} 260^{\circ} \mathrm{C}
\end{aligned}$$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
02:10

Problem 66

Sodium carbonate, an important chemical used in the production of glass, is made from sodium hydrogen carbonate by the reaction $2 \mathrm{NaHCO}_{3}(\mathrm{s}) \rightleftharpoons \mathrm{Na}_{2} \mathrm{CO}_{3}(\mathrm{s})+\mathrm{CO}_{2}(\mathrm{g})+\mathrm{H}_{2} \mathrm{O}(\mathrm{g})$
Data for the temperature variation of $K_{\mathrm{p}}$ for this reaction are $K_{\mathrm{p}}=1.66 \times 10^{-5}$ at $30^{\circ} \mathrm{C} ; 3.90 \times 10^{-4} \mathrm{at}$
$50^{\circ} \mathrm{C} ; 6.27 \times 10^{-3}$ at $70^{\circ} \mathrm{C} ;$ and $2.31 \times 10^{-1}$ at $100^{\circ} \mathrm{C}$
(a) Plot a graph similar to Figure $19-12,$ and determine $\Delta H^{\circ}$ for the reaction.
(b) Calculate the temperature at which the total gas pressure above a mixture of $\mathrm{NaHCO}_{3}(\mathrm{s})$ and $\mathrm{Na}_{2} \mathrm{CO}_{3}(\mathrm{s})$ is $2.00 \mathrm{atm}$.

Lottie Adams
Lottie Adams
Numerade Educator
06:24

Problem 67

Titanium is obtained by the reduction of $\mathrm{TiCl}_{4}(1)$ which in turn is produced from the mineral rutile $\left(\mathrm{TiO}_{2}\right)$
(a) With data from Appendix D, determine $\Delta G^{\circ}$ at
298 K for this reaction.
$$\mathrm{TiO}_{2}(\mathrm{s})+2 \mathrm{Cl}_{2}(\mathrm{g}) \longrightarrow \mathrm{TiCl}_{4}(1)+\mathrm{O}_{2}(\mathrm{g})$$
(b) Show that the conversion of $\mathrm{TiO}_{2}(\mathrm{s})$ to $\mathrm{TiCl}_{4}(1)$ with reactants and products in their standard states, is spontaneous at $298 \mathrm{K}$ if the reaction in (a) is coupled with the reaction
$$2 \mathrm{CO}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \longrightarrow 2 \mathrm{CO}_{2}(\mathrm{g})$$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
01:29

Problem 68

Following are some standard Gibbs energies of formation, $\Delta G_{f}^{2},$ per mole of metal oxide at $1000 \mathrm{K}: \mathrm{NiO},$ $-115 \mathrm{kJ} ; \mathrm{MnO},-280 \mathrm{kJ} ; \mathrm{TiO}_{2},-630 \mathrm{kJ} .$ The standard
Gibbs energy of formation of $\mathrm{CO}$ at $1000 \mathrm{K}$ is $-250 \mathrm{kJ}$ per mol CO. Use the method of coupled reactions (page 851 ) to determine which of these metal oxides can be reduced to the metal by a spontaneous reaction with carbon at $1000 \mathrm{K}$ and with all reactants and products in their standard states.

Anthony Han
Anthony Han
Numerade Educator
01:37

Problem 69

In biochemical reactions the phosphorylation of amino acids is an important step. Consider the following two reactions and determine whether the phosphorylation of arginine with ATP is spontaneous.
$$\begin{array}{c}
\mathrm{ATP}+\mathrm{H}_{2} \mathrm{O} \longrightarrow \mathrm{ADP}+\mathrm{P} \quad \Delta G^{\circ \prime}=-31.5 \mathrm{kJ} \mathrm{mol}^{-1} \\
\text {arginine }+\mathrm{P} \longrightarrow \text { phosphorarginine }+\mathrm{H}_{2} \mathrm{O} \\
\Delta G^{\circ \prime}=33.2 \mathrm{kJ} \mathrm{mol}^{-1}
\end{array}$$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
02:12

Problem 70

The synthesis of glutamine from glutamic acid is given by Glu $^{-}+\mathrm{NH}_{4}^{+} \longrightarrow \mathrm{Gln}+\mathrm{H}_{2} \mathrm{O}$. The Gibbs
energy for this reaction at $\mathrm{pH}=7$ and $T=310 \mathrm{K}$ is $\Delta G^{\circ \prime}=14.8 \mathrm{kJ} \mathrm{mol}^{-1} .$ Will this reaction be sponta-
neous if coupled with the hydrolysis of ATP?
$\mathrm{ATP}+\mathrm{H}_{2} \mathrm{O} \longrightarrow \mathrm{ADP}+\mathrm{P}$
$$\Delta G^{\circ \prime}=-31.5 \mathrm{kJ} \mathrm{mol}-1$$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
05:27

Problem 71

Use data from Appendix D to estimate (a) the normal boiling point of mercury and (b) the vapor pressure of mercury at $25^{\circ} \mathrm{C}$.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
01:42

Problem 72

Consider the vaporization of water: $\mathrm{H}_{2} \mathrm{O}(1) \longrightarrow$ $\mathrm{H}_{2} \mathrm{O}(\mathrm{g})$ at $100^{\circ} \mathrm{C},$ with $\mathrm{H}_{2} \mathrm{O}(1)$ in its standard state,
but with the partial pressure of $\mathrm{H}_{2} \mathrm{O}(\mathrm{g})$ at $2.0 \mathrm{atm}$ Which of the following statements about this vaporization at $100^{\circ} \mathrm{C}$ are true? (a) $\Delta G^{\circ}=0,$ (b) $\Delta G=0$
(c) $\Delta G^{\circ}>0,$ (d) $\Delta G>0 ?$ Explain.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
07:05

Problem 73

At $298 \mathrm{K}, 1.00 \mathrm{mol} \mathrm{BrCl}(\mathrm{g})$ is introduced into a $10.0 \mathrm{L}$
vessel, and equilibrium is established in the reac$\operatorname{tion} \operatorname{BrCl}(\mathrm{g}) \rightleftharpoons \frac{1}{2} \mathrm{Br}_{2}(\mathrm{g})+\frac{1}{2} \mathrm{Cl}_{2}(\mathrm{g}) .$ Calculate the
amounts of each of the three gases present when equilibrium is established. [Hint: Use data from Appendix D as necessary.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
00:59

Problem 74

Use data from Appendix $D$ and other information from this chapter to estimate the temperature at which the dissociation of $\mathrm{I}_{2}(\mathrm{g})$ becomes appreciable [for example, with the $\mathrm{I}_{2}(\mathrm{g}) 50 \%$ dissociated into $\mathrm{I}(\mathrm{g})$ at 1 atm total pressure.

Lottie Adams
Lottie Adams
Numerade Educator
02:06

Problem 75

The following table shows the enthalpies and Gibbs energies of formation of three metal oxides at $25^{\circ} \mathrm{C}$.
(a) Which of these oxides can be most readily decomposed to the free metal and $\mathrm{O}_{2}(\mathrm{g}) ?$
(b) For the oxide that is most easily decomposed, to what temperature must it be heated to produce $\mathrm{O}_{2}(\mathrm{g})$ at 1.00 atm pressure?
$$\begin{array}{lll}
\hline & \Delta \mathrm{H}_{7}, \mathrm{kJ} \mathrm{mol}^{-1} & \Delta \mathrm{G}_{7}, \mathrm{kJ} \mathrm{mol}^{-1} \\
\hline \mathrm{PbO}(\mathrm{red}) & -219.0 & -188.9 \\
\mathrm{Ag}_{2} \mathrm{O} & -31.05 & -11.20 \\
\mathrm{ZnO} & -348.3 & -318.3 \\
\hline
\end{array}$$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
06:16

Problem 76

The following data are given for the two solid forms of $\mathrm{HgI}_{2}$ at $298 \mathrm{K}$. $$\begin{array}{llll}
\hline & \Delta H_{f}^{\circ} & \Delta G_{f,}^{\circ} & S^{\circ} \\
& \text { kJ mol }^{-1} & \text {kJ mol }^{-1} & \text {J mol }^{-1} \text {K }^{-1} \\
\hline \mathrm{HgI}_{2} \text { (red) } & -105.4 & -101.7 & 180 \\
\mathrm{Hg} \mathrm{I}_{2} \text { (yellow) } & -102.9 & (?) & (?) \\
\hline
\end{array}$$
Estimate values for the two missing entries. To do this, assume that for the transition $\mathrm{HgI}_{2}(\mathrm{red}) \longrightarrow$ $\mathrm{HgI}_{2}(\text { yellow }),$ the values of $\Delta H^{\circ}$ and $\Delta S^{\circ}$ at $25^{\circ} \mathrm{C}$ have the same values that they do at the equilibrium temperature of $127^{\circ} \mathrm{C}$.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
07:46

Problem 77

Oxides of nitrogen are produced in high-temperature combustion processes. The essential reaction is $\mathrm{N}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{NO}(\mathrm{g}) .$ At what approximate temperature will an equimolar mixture of $\mathrm{N}_{2}(\mathrm{g})$ and $\mathrm{O}_{2}(\mathrm{g})$ be $1.0 \%$ converted to $\mathrm{NO}(\mathrm{g}) ?[$ Hint: Use data from Appendix D as necessary.]

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
03:26

Problem 78

Use the following data, as appropriate, to estimate the molarity of a saturated aqueous solution of $\operatorname{Sr}\left(\mathrm{IO}_{3}\right)_{2}$.
$$\begin{array}{lcll}
\hline & \begin{array}{l}
\Delta H_{f,}^{0} \\
\mathrm{kJmol}^{-1}
\end{array} & \begin{array}{l}
\Delta G_{f,}^{\circ} \\
\mathrm{kJ} \mathrm{mol}^{-1}
\end{array} & \begin{array}{l}
S_{^{\prime}}^{\circ} \\
\mathrm{J} \mathrm{mol}^{-1} \mathrm{K}^{-1}
\end{array} \\
\hline \operatorname{Sr}\left(\mathrm{IO}_{3}\right)_{2}(\mathrm{s}) & -1019.2 & -855.1 & 234 \\
\mathrm{Sr}^{2+}(\mathrm{aq}) & -545.8 & -599.5 & -32.6 \\
\mathrm{IO}_{3}^{-}(\mathrm{aq}) & -221.3 & -128.0 & 118.4 \\
\hline
\end{array}$$

A. Elizabeth Hildreth
A. Elizabeth Hildreth
Numerade Educator
08:41

Problem 79

Use the following data together with other data from the text to determine the temperature at which the equilibrium pressure of water vapor above the two solids in the following reaction is 75 Torr.
$$\mathrm{CuSO}_{4} \cdot 3 \mathrm{H}_{2} \mathrm{O}(\mathrm{s}) \rightleftharpoons \mathrm{CuSO}_{4} \cdot \mathrm{H}_{2} \mathrm{O}(\mathrm{s})+2 \mathrm{H}_{2} \mathrm{O}(\mathrm{g})$$
$$\begin{array}{llll}
\hline & \Delta H_{f,}^{\circ} & \Delta G_{f,}^{\circ} & S_{^{\prime}}^{\circ} \\
& \mathrm{kJmol}^{-1} & \mathrm{kJ} \mathrm{mol}^{-1} & \mathrm{J} \mathrm{mol}^{-1} \mathrm{K}^{-1} \\
\hline \mathrm{CuSO}_{4} \cdot 3 \mathrm{H}_{2} \mathrm{O}(\mathrm{s}) & -1684.3 & -1400.0 & 221.3 \\
\mathrm{CuSO}_{4} \cdot \mathrm{H}_{2} \mathrm{O}(\mathrm{s}) & -1085.8 & -918.1 & 146.0 \\
\hline
\end{array}$$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
01:25

Problem 80

For the dissociation of $\mathrm{CaCO}_{3}(\mathrm{s})$ at $25^{\circ} \mathrm{C}, \mathrm{CaCO}_{3}(\mathrm{s})$
$\rightleftharpoons \mathrm{CaO}(\mathrm{s})+\mathrm{CO}_{2}(\mathrm{g}) \Delta G^{\circ}=+131 \mathrm{kJ} \mathrm{mol}^{-1} .$ A sample of pure $\mathrm{CaCO}_{3}(\mathrm{s})$ is placed in a flask and connected to an ultrahigh vacuum system capable of reducing the pressure to $10^{-9} \mathrm{mmHg}$
(a) Would $\mathrm{CO}_{2}(\mathrm{g})$ produced by the decomposition of $\mathrm{CaCO}_{3}(\mathrm{s})$ at $25^{\circ} \mathrm{C}$ be detectable in the vacuum system at $25^{\circ} \mathrm{C} ?$
(b) What additional information do you need to determine $P_{\mathrm{CO}_{2}}$ as a function of temperature?
(c) With necessary data from Appendix D, determine the minimum temperature to which $\mathrm{CaCO}_{3}(\mathrm{s})$ would have to be heated for $\mathrm{CO}_{2}(\mathrm{g})$ to become detectable in the vacuum system.

Akhil Choudhary
Akhil Choudhary
Numerade Educator
16:59

Problem 81

Introduced into a 1.50 L flask is 0.100 mol of $\mathrm{PCl}_{5}(\mathrm{g})$ the flask is held at a temperature of $227^{\circ} \mathrm{C}$ until equilibrium is established. What is the total pressure of the gases in the flask at this point?
$$\mathrm{PCl}_{5}(\mathrm{g}) \rightleftharpoons \mathrm{PCl}_{3}(\mathrm{g})+\mathrm{Cl}_{2}(\mathrm{g})$$
[Hint: Use data from Appendix D and appropriate relationships from this chapter.]

Carina Carlos
Carina Carlos
Numerade Educator
03:53

Problem 82

From the data given in Exercise $66,$ estimate a value of $\Delta S^{\circ}$ at $298 \mathrm{K}$ for the reaction
$2 \mathrm{NaHCO}_{3}(\mathrm{s}) \longrightarrow \mathrm{Na}_{2} \mathrm{CO}_{3}(\mathrm{s})+\mathrm{H}_{2} \mathrm{O}(\mathrm{g})+\mathrm{CO}_{2}(\mathrm{g})$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
02:42

Problem 83

The normal boiling point of cyclohexane, $\mathrm{C}_{6} \mathrm{H}_{12}$, is
$80.7^{\circ} \mathrm{C} .$ Estimate the temperature at which the vapor pressure of cyclohexane is $100.0 \mathrm{mmHg}$.

Aadit Sharma
Aadit Sharma
Numerade Educator
03:16

Problem 84

The term thermodynamic stability refers to the sign of $\Delta G_{f}^{\circ} .$ If $\Delta G_{f}^{\circ}$ is negative, the compound is stable with respect to decomposition into its elements. Use the data in Appendix D to determine whether $\mathrm{Ag}_{2} \mathrm{O}(\mathrm{s})$ is thermodynamically stable at (a) $25^{\circ} \mathrm{C}$ and $(\mathrm{b}) 200^{\circ} \mathrm{C}$.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
03:10

Problem 85

At $0^{\circ} \mathrm{C},$ ice has a density of $0.917 \mathrm{g} \mathrm{mL}^{-1}$ and an absolute entropy of $37.95 \mathrm{Jmol}^{-1} \mathrm{K}^{-1}$. At this temperature, liquid water has a density of $1.000 \mathrm{g} \mathrm{mL}^{-1}$ and an absolute entropy of $59.94 \mathrm{Jmol}^{-1} \mathrm{K}^{-1}$. The pressure corresponding to these values is 1 bar. Calculate $\Delta G$ $\Delta G^{\circ}, \Delta S^{\circ},$ and $\Delta H^{\circ}$ for the melting of two moles of ice at its normal melting point.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
08:16

Problem 86

The decomposition of the poisonous gas phosgene is represented by the equation $\mathrm{COCl}_{2}(\mathrm{g}) \rightleftharpoons \mathrm{CO}(\mathrm{g})+$
$\mathrm{Cl}_{2}(\mathrm{g}) .$ Values of $K_{\mathrm{p}}$ for this reaction are $K_{\mathrm{p}}=$ $6.7 \times 10^{-9}$ at $99.8^{\circ} \mathrm{C}$ and $K_{\mathrm{p}}=4.44 \times 10^{-2}$ at $395^{\circ} \mathrm{C}$
At what temperature is $\mathrm{COCl}_{2} 15 \%$ dissociated when the total gas pressure is maintained at 1.00 atm?

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
View

Problem 87

Use data from Appendix D to estimate the aqueous solubility, in milligrams per liter, of $\mathrm{AgBr}(\mathrm{s})$ at $100^{\circ} \mathrm{C}$.

Susan Hallstrom
Susan Hallstrom
Numerade Educator
02:24

Problem 88

The standard molar entropy of solid hydrazine at its melting point of $1.53^{\circ} \mathrm{C}$ is $67.15 \mathrm{Jmol}^{-1} \mathrm{K}^{-1}$. The enthalpy of fusion is $12.66 \mathrm{kJmol}^{-1} .$ For $\mathrm{N}_{2} \mathrm{H}_{4}(1)$ in the interval from $1.53^{\circ} \mathrm{C}$ to $298.15 \mathrm{K}$, the molar heat capacity at constant pressure is given by the expression $C_{p}=97.78+0.0586(T-280) .$ Determine the standard molar entropy of $\mathrm{N}_{2} \mathrm{H}_{4}(\mathrm{l})$ at $298.15 \mathrm{K}$. [Hint: The heat absorbed to produce an infinitesimal change in the temperature of a substance is $d q_{\mathrm{rev}}=C_{p} d T$.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
03:27

Problem 89

Use the following data to estimate the standard molar entropy of gaseous benzene at $298.15 \mathrm{K} ;$ that is, $S^{\circ}\left[\mathrm{C}_{6} \mathrm{H}_{6}(\mathrm{g}, 1 \mathrm{atm})\right] .$ For $\mathrm{C}_{6} \mathrm{H}_{6}(\mathrm{s}, 1 \mathrm{atm})$ at its melting
point of $5.53^{\circ} \mathrm{C}, S^{\circ}$ is $128.82 \mathrm{Jmol}^{-1} \mathrm{K}^{-1}$. The enthalpy
of fusion is $9.866 \mathrm{kJ} \mathrm{mol}^{-1} .$ From the melting point to 298.15 K, the average heat capacity of liquid benzene is $134.0 \mathrm{JK}^{-1} \mathrm{mol}^{-1} .$ The enthalpy of vaporization of $\mathrm{C}_{6} \mathrm{H}_{6}(1)$ at $298.15 \mathrm{K}$ is $33.85 \mathrm{kJ} \mathrm{mol}^{-1},$ and in the vapor-
ization, $\mathrm{C}_{6} \mathrm{H}_{6}(\mathrm{g})$ is produced at a pressure of 95.13 Torr. Imagine that this vapor could be compressed to 1 atm pressure without condensing and while behaving as an ideal gas. Calculate $S^{\circ}\left[\mathrm{C}_{6} \mathrm{H}_{6}(\mathrm{g}, 1 \text { atm) }] .[ \text { Hint: Refer to }\right.$ Exercise $88,$ and note the following: For infinitesimal quantities, $d S=d q / d T ;$ for the compression of an ideal gas, $d q=-d w ;$ and for pressure-volume work, $d w=-P d V$.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
04:33

Problem 90

On page 822 the terms states and microstates were introduced. Consider a system that has four states (i.e., energy levels), with energy $\varepsilon=0,1,2,$ and 3 energy units, and three particles labeled $A, B,$ and $C .$ The total energy of the system, in energy units, is 3 . How many microstates can be generated?

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
01:18

Problem 91

In Figure $19-7,$ page $830,$ the temperature dependence of the standard molar entropy for chloroform is plotted. (a) Explain why the slope for the standard molar entropy of the solid is greater than the slope for the standard molar entropy of the liquid, which is greater than the slope for the standard molar entropy of the gas. (b) Explain why the change in the standard molar entropy from solid to liquid is smaller than that for the liquid to gas.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
03:32

Problem 92

The following data are from a laboratory experiment that examines the relationship between solubility and thermodynamics. In this experiment $\mathrm{KNO}_{3}(\mathrm{s})$ is placed in a test tube containing some water. The solution is heated until all the $\mathrm{KNO}_{3}(\mathrm{s})$ is dissolved and then allowed to cool. The temperature at which crystals appear is then measured. From this experiment we can determine the equilibrium constant, Gibbs energy, enthalpy, and entropy for the reaction. Use the following data to calculate $\Delta G, \Delta H,$ and $\Delta S$ for the dissolution of $\mathrm{KNO}_{3}(\mathrm{s}) .$ (Assume the initial mass of $\left.\mathrm{KNO}_{3}(\mathrm{s}) \text { was } 20.2 \mathrm{g} .\right)$$$\begin{array}{cc}
\hline \text { Total Volume, } \mathrm{mL} & \begin{array}{c}
\text { Temperature Crystals } \\
\text { Formed, } \mathrm{K}
\end{array} \\
\hline 25.0 & 340 \\
29.2 & 329 \\
33.4 & 320 \\
37.6 & 313 \\
41.8 & 310 \\
46.0 & 306 \\
51.0 & 303 \\
\hline
\end{array}$$

Bin Chen
Bin Chen
Numerade Educator
06:29

Problem 93

A tabulation of more precise thermodynamic data than are presented in Appendix D lists the following values for $\mathrm{H}_{2} \mathrm{O}(\mathrm{l})$ and $\mathrm{H}_{2} \mathrm{O}(\mathrm{g})$ at $298.15 \mathrm{K},$ at a standard state pressure of 1 bar.
$$\begin{array}{llll}
\hline & \Delta H_{f}^{\circ}, & \Delta G_{f,}^{\circ} & S_{\prime}^{\circ} \\
& \text { kJ mol }^{-1} & \text {kJ mol }^{-1} & \text {J mol }^{-1} \text {K }^{-1} \\
\hline \mathrm{H}_{2} \mathrm{O}(1) & -285.830 & -237.129 & 69.91 \\
\mathrm{H}_{2} \mathrm{O}(\mathrm{g}) & -241.818 & -228.572 & 188.825 \\
\hline
\end{array}$$
(a) Use these data to determine, in two different ways, $\Delta G^{\circ}$ at $298.15 \mathrm{K}$ for the vaporization:
$\mathrm{H}_{2} \mathrm{O}(1,1 \mathrm{bar}) \rightleftharpoons \mathrm{H}_{2} \mathrm{O}(\mathrm{g}, 1 \mathrm{bar}) .$ The value you
obtain will differ slightly from that on page 838 because here, the standard state pressure is 1 bar, and there, it is 1 atm.
(b) Use the result of part (a) to obtain the value of $K$ for this vaporization and, hence, the vapor pressure of water at $298.15 \mathrm{K}$
(c) The vapor pressure in part (b) is in the unit bar. Convert the pressure to millimeters of mercury.
(d) Start with the value $\Delta G^{\circ}=8.590 \mathrm{kJ}$, given on page 838 and calculate the vapor pressure of water at 298.15 K in a fashion similar to that in parts (b) and
(c). In this way, demonstrate that the results obtained in a thermodynamic calculation do not depend on the convention we choose for the standard state pressure, as long as we use standard state thermodynamic data consistent with that choice.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
02:12

Problem 94

The graph shows how $\Delta G^{\circ}$ varies with temperature for three different oxidation reactions: the oxidations of $\mathrm{C}$ (graphite), $\mathrm{Zn},$ and $\mathrm{Mg}$ to $\mathrm{CO}, \mathrm{ZnO},$ and $\mathrm{MgO}$ respectively. Such graphs as these can be used to show the temperatures at which carbon is an effective reducing agent to reduce metal oxides to the free metals. As a result, such graphs are important to metallurgists. Use these graphs to answer the following questions.
(a) Why can Mg be used to reduce ZnO to Zn at all temperatures, but Zn cannot be used to reduce $\mathrm{MgO}$ to Mg at any temperature?
(b) Why can C be used to reduce ZnO to Zn at some temperatures but not at others? At what temperatures can carbon be used to reduce zinc oxide?
(c) Is it possible to produce $\mathrm{Zn}$ from $\mathrm{ZnO}$ by its direct decomposition without requiring a coupled reaction? If
so, at what approximate temperatures might this occur?
(d) Is it possible to decompose $\mathrm{CO}$ to $\mathrm{C}$ and $\mathrm{O}_{2}$ in a spontaneous reaction? Explain.$\mathbf{} \Delta G^{\circ}$ for three reactions as a function of temperature. The reactions are indicated by the equations written above the graphs. The points noted by arrows are the melting points (mp) and boiling points (bp) of zinc and magnesium. (e) To the set of graphs, add straight lines representing the reactions
$$\begin{array}{r}
\mathrm{C}(\text { graphite })+\mathrm{O}_{2}(\mathrm{g}) \longrightarrow \mathrm{CO}_{2}(\mathrm{g}) \\
\quad 2 \mathrm{CO}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \longrightarrow 2 \mathrm{CO}_{2}(\mathrm{g})
\end{array}$$ given that the three lines representing the formation of oxides of carbon intersect at about $800^{\circ} \mathrm{C}$. [Hint:
At what other temperature can you relate $\Delta G^{\circ}$ and temperature? The slopes of the three lines described above differ sharply. Explain why this is so-that is, explain the slope of each line in terms of principles governing Gibbs energy change.
(f) The graphs for the formation of oxides of other metals are similar to the ones shown for $\mathrm{Zn}$ and $\mathrm{Mg}$; that is, they all have positive slopes. Explain why carbon is such a good reducing agent for the reduction of metal oxides.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
08:35

Problem 95

In a heat engine, heat $\left(q_{\mathrm{h}}\right)$ is absorbed by a working substance (such as water) at a high temperature $\left(T_{\mathrm{h}}\right)$ Part of this heat is converted to work $(w),$ and the rest $\left(q_{1}\right)$ is released to the surroundings at the lower temperature ( $T_{1}$ ). The efficiency of a heat engine is the ratio $w / q_{\mathrm{h}}$. The second law of thermodynamics establishes the following equation for the maximum efficiency of a heat engine, expressed on a percentage basis.
$$\text { efficiency }=\frac{w}{q_{\mathrm{h}}} \times 100 \%=\frac{T_{\mathrm{h}}-T_{1}}{T_{\mathrm{h}}} \times 100 \%$$ In a particular electric power plant, the steam leaving a steam turbine is condensed to liquid water at
$41^{\circ} \mathrm{C}\left(T_{1}\right)$ and the water is returned to the boiler to be regenerated as steam. If the system operates at $36 \%$ efficiency,
(a) What is the minimum temperature of the steam
$\left[\mathrm{H}_{2} \mathrm{O}(\mathrm{g})\right]$ used in the plant?
(b) Why is the actual steam temperature probably higher than that calculated in part (a)?
(c) Assume that at $T_{\mathrm{h}}$ the $\mathrm{H}_{2} \mathrm{O}(\mathrm{g})$ is in equilibrium with $\mathrm{H}_{2} \mathrm{O}(1) .$ Estimate the steam pressure at the temperature calculated in part (a).
(d) Is it possible to devise a heat engine with greater than 100 percent efficiency? With 100 percent efficiency? Explain.

Eduard Sanchez
Eduard Sanchez
Numerade Educator
04:46

Problem 96

The Gibbs energy available from the complete combustion of 1 mol of glucose to carbon dioxide and water is $$\begin{array}{r}
\mathrm{C}_{6} \mathrm{H}_{12} \mathrm{O}_{6}(\mathrm{aq})+6 \mathrm{O}_{2}(\mathrm{g}) \longrightarrow 6 \mathrm{CO}_{2}(\mathrm{g})+6 \mathrm{H}_{2} \mathrm{O}(\mathrm{l}) \\
\Delta G^{\circ}=-2870 \mathrm{kJ} \mathrm{mol}^{-1}
\end{array}$$ (a) Under biological standard conditions, compute the maximum number of moles of ATP that could form from ADP and phosphate if all the energy of combustion of 1 mol of glucose could be utilized.
(b) The actual number of moles of ATP formed by a cell under aerobic conditions (that is, in the presence of oxygen) is about $38 .$ Calculate the efficiency of energy conversion of the cell.
(c) Consider these typical physiological conditions.
$$\begin{array}{l}
P_{\mathrm{CO}_{2}}=0.050 \mathrm{bar} ; P_{\mathrm{O}_{2}}=0.132 \mathrm{bar} \\
{[\mathrm{glucose}]=1.0 \mathrm{mg} / \mathrm{mL} ; \mathrm{pH}=7.0} \\
{[\mathrm{ATP}]=[\mathrm{ADP}]=\left[P_{\mathrm{i}}\right]=0.00010 \mathrm{M}}
\end{array}$$
Calculate $\Delta G$ for the conversion of 1 mol ADP to ATP and $\Delta G$ for the oxidation of 1 mol glucose under these conditions.
(d) Calculate the efficiency of energy conversion for the cell under the conditions given in part (c). Compare this efficiency with that of a diesel engine that attains $78 \%$ of the theoretical efficiency operating with $T_{\mathrm{h}}=1923 \mathrm{K}$ and $T_{1}=873 \mathrm{K} .$ Suggest a reason for your result. [ Hint: See Feature Problem 95.]

Rabeya Zahid
Rabeya Zahid
Numerade Educator
02:55

Problem 97

The entropy of materials at $T=0 \mathrm{K}$ should be zero; however, for some substances, such as $\mathrm{CO}$ and $\mathrm{H}_{2} \mathrm{O}$ this is not true. The difference between the measured value and expected value of zero is known as residual entropy. (a) Calculate the residual entropy for one mole of CO by using the Boltzmann equation for entropy. (b) Calculate the residual entropy for one mole of $\mathrm{H}_{2} \mathrm{O}$ in the same manner.

Henry R
Henry R
Numerade Educator
02:06

Problem 98

In your own words, define the following symbols:
(a) $\Delta S_{\text {univ }} ;$ (b) $\Delta G_{f}^{0} ;$ (c) $K$.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
02:21

Problem 99

Briefly describe each of the following ideas, methods, or phenomena: (a) absolute molar entropy;
(b) coupled reactions; (c) Trouton's rule; (d) evaluation of an equilibrium constant from tabulated thermodynamic data.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
03:04

Problem 100

Explain the important distinctions between each of the following pairs: (a) spontaneous and nonspontaneous processes; (b) the second and third laws of thermodynamics; (c) $\Delta G$ and $\Delta G^{\circ}$.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
02:09

Problem 101

For a process to occur spontaneously, (a) the entropy of the system must increase; (b) the entropy of the surroundings must increase; (c) both the entropy of the system and the entropy of the surroundings must increase; (d) the net change in entropy of the system and surroundings considered together must be a positive quantity; (e) the entropy of the universe must remain constant.

Alexander Clippinger
Alexander Clippinger
Numerade Educator
01:31

Problem 102

The Gibbs energy change of a reaction can be used to assess (a) how much heat is absorbed from the surroundings; (b) how much work the system does on the surroundings; (c) the net direction in which the reaction occurs to reach equilibrium; (d) the proportion of the heat evolved in an exothermic reaction that can be converted to various forms of work.

Jesse Leeder
Jesse Leeder
Numerade Educator
02:04

Problem 103

The reaction, $2 \mathrm{Cl}_{2} \mathrm{O}(\mathrm{g}) \longrightarrow 2 \mathrm{Cl}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \Delta H=$
$-161 \mathrm{kJ},$ is expected to be (a) spontaneous at all temperatures; (b) spontaneous at low temperatures, but nonspontaneous at high temperatures; (c) nonspontaneous at all temperatures; (d) spontaneous at high temperatures only.

Jesse Leeder
Jesse Leeder
Numerade Educator
01:06

Problem 104

If $\Delta G^{\circ}=0$ for a reaction, it must also be true that
(a) $K=0 ;$ (b) $K=1 ;$ (c) $\Delta H^{\circ}=0 ;$ (d) $\Delta S^{\circ}=0$
(e) the equilibrium activities of the reactants and products do not depend on the initial conditions.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
02:03

Problem 105

Two correct statements about the reversible reaction $\mathrm{N}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \rightleftharpoons 2 \mathrm{NO}(\mathrm{g})$ are $(\mathrm{a}) K=K_{\mathrm{p}}$
(b) the equilibrium amount of NO increases with an increased total gas pressure; (c) the equilibrium amount of NO increases if an equilibrium mixture is transferred from a $10.0 \mathrm{L}$ container to a $20.0 \mathrm{L}$ container; (d) $K=K_{c} ;$ (e) the composition of an equilibrium mixture of the gases is independent of the temperature.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
02:05

Problem 106

Suppose a graph similar to (Figure $19-9$ ) were drawn for the process $\mathrm{I}_{2}(\mathrm{s}) \longrightarrow \mathrm{I}_{2}(1)$ at 1 atm.
(a) Refer to Figure $12-27$ and determine the temperature at which the two lines would intersect.
(b) What would be the value of $\Delta G^{\circ}$ at this temperature? Explain.

Lottie Adams
Lottie Adams
Numerade Educator
02:08

Problem 107

Without performing detailed calculations, indicate whether any of the following reactions would occur to a measurable extent at $298 \mathrm{K}$.
(a) Conversion of dioxygen to ozone:
$$3 \mathrm{O}_{2}(\mathrm{g}) \longrightarrow 2 \mathrm{O}_{3}(\mathrm{g})$$
(b) Dissociation of $\mathrm{N}_{2} \mathrm{O}_{4}$ to $\mathrm{NO}_{2}:$
$$\mathrm{N}_{2} \mathrm{O}_{4}(\mathrm{g}) \longrightarrow 2 \mathrm{NO}_{2}(\mathrm{g})$$
(c) Formation of BrCl:
$$\mathrm{Br}_{2}(1)+\mathrm{Cl}_{2}(\mathrm{g}) \longrightarrow 2 \mathrm{BrCl}(\mathrm{g})$$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
01:13

Problem 108

Explain briefly why
(a) the change in entropy in a system is not always a suitable criterion for spontaneous change;
(b) $\Delta G^{\circ}$ is so important in dealing with the question of spontaneous change, even though the conditions employed in a reaction are very often nonstandard.

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
02:17

Problem 109

A handbook lists the following standard a handbook lists the following standard enthalpies of formation at $298 \mathrm{K}$ for cyclopentane, $\mathrm{C}_{5} \mathrm{H}_{10}: \quad \Delta H_{\mathrm{f}}^{\mathrm{g}}\left[\mathrm{C}_{5} \mathrm{H}_{10}(1)\right]=-105.9 \mathrm{kJ} / \mathrm{mol} \quad$ and
$\Delta H_{\mathrm{f}}^{\mathrm{o}}\left[\mathrm{C}_{5} \mathrm{H}_{10}(\mathrm{g})\right]=-77.2 \mathrm{kJ} / \mathrm{mol}$
(a) Estimate the normal boiling point of cyclopentane.
(b) Estimate $\Delta G^{\circ}$ for the vaporization of cyclopentane at $298 \mathrm{K}$.
(c) Comment on the significance of the sign of $\Delta G^{\circ}$
at $298 \mathrm{K}$

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
05:34

Problem 110

Consider the reaction $\mathrm{NH}_{4} \mathrm{NO}_{3}(\mathrm{s}) \longrightarrow \mathrm{N}_{2} \mathrm{O}(\mathrm{g})+$
$2 \mathrm{H}_{2} \mathrm{O}(1)$ at $298 \mathrm{K}$
(a) Is the forward reaction endothermic or exothermic?
(b) What is the value of $\Delta G^{\circ}$ at $298 \mathrm{K} ?$
(c) What is the value of $K$ at $298 \mathrm{K} ?$
(d) Does the reaction tend to occur spontaneously at temperatures above $298 \mathrm{K},$ below $298 \mathrm{K},$ both, or neither?

Banhishikha Sinha
Banhishikha Sinha
Numerade Educator
02:15

Problem 111

Which of the following diagrams represents an equilibrium constant closest to $1 ?$

Himanshu Kushwaha
Himanshu Kushwaha
Numerade Educator
02:05

Problem 112

At room temperature and normal atmospheric pressure, is the entropy of the universe positive, negative, or zero for the transition of carbon dioxide solid to liquid?

Pronoy Sinha
Pronoy Sinha
Numerade Educator