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Problem 1

Consider an equilibrium mixture of four chemicals \((\mathrm{A}, \mathrm{B}, \mathrm{C},\), and \(\mathrm{D}\), all gases) reacting in a closed flask according to the equation: $$ \mathrm{A}(g)+\mathrm{B}(g) \rightleftharpoons \mathrm{C}(g)+\mathrm{D}(g) $$ a. You add more \(\mathrm{A}\) to the flask. How does the concentration of each chemical compare to its original concentration after equilibrium is reestablished? Justify your answer. b. You have the original setup at equilibrium, and you add more \(\mathrm{D}\) to the flask. How does the concentration of each chemical compare to its original concentration after equilibrium is reestablished? Justify your answer.

Problem 8

Le Châtelier's principle is stated (Section \(13.7)\) as follows: "If a change is imposed on a system at equilibrium, the position of the equilibrium will shift in a direction that tends to reduce that change." The system \(\mathrm{N}_{2}(g)+3 \mathrm{H}_{2}(g) \rightleftharpoons 2 \mathrm{NH}_{3}(g)\) is used as an example in which the addition of nitrogen gas at equilibrium results in a decrease in \(\mathrm{H}_{2}\) concentration and an increase in \(\mathrm{NH}_{3}\) concentration. In the experiment the volume is assumed to be constant. On the other hand, if \(\mathrm{N}_{2}\) is added to the reaction system in a container with a piston so that the pressure can be held constant, the amount of \(\mathrm{NH}_{3}\) actually could decrease and the concentration of \(\mathrm{H}_{2}\) would increase as equilibrium is reestablished. Explain how this can happen. Also, if you consider this same system at equilibrium, the addition of an inert gas, holding the pressure constant, does affect the equilibrium position. Explain why the addition of an inert gas to this system in a rigid container does not affect the equilibrium position.

Problem 9

The value of the equilibrium constant \(K\) depends on which of the following (more than one answer may be correct)? a. the initial concentrations of the reactants b. the initial concentrations of the products c. the temperature of the system d. the nature of the reactants and products Explain.

Problem 13

Suppose a reaction has the equilibrium constant \(K=1.3 \times 10^{8}\). What does the magnitude of this constant tell you about the relative concentrations of products and reactants that will be present once equilibrium is reached? Is this reaction likely to be a good source of the products?

Problem 20

Which of the following statements is(are) true? Correct the false statement(s). a. When a reactant is added to a system at equilibrium at a given temperature, the reaction will shift right to reestablish equilibrium. b. When a product is added to a system at equilibrium at a given temperature, the value of \(K\) for the reaction will increase when equilibrium is reestablished. c. When temperature is increased for a reaction at equilibrium, the value of \(K\) for the reaction will increase. d. When the volume of a reaction container is increased for a system at equilibrium at a given temperature, the reaction will shift left to reestablish equilibrium. e. Addition of a catalyst (a substance that increases the speed of the reaction) has no effect on the equilibrium position.

Problem 23

At a given temperature, \(K=1.3 \times 10^{-2}\) for the reaction $$ \mathrm{N}_{2}(g)+3 \mathrm{H}_{2}(g) \rightleftharpoons 2 \mathrm{NH}_{3}(g) $$ Calculate values of \(K\) for the following reactions at this temperature. a. \(\frac{1}{2} \mathrm{~N}_{2}(g)+\frac{3}{2} \mathrm{H}_{2}(g) \rightleftharpoons \mathrm{NH}_{3}(g)\) b. \(2 \mathrm{NH}_{3}(g) \rightleftharpoons \mathrm{N}_{2}(g)+3 \mathrm{H}_{2}(g)\) c. \(\mathrm{NH}_{3}(g) \rightleftharpoons \frac{1}{2} \mathrm{~N}_{2}(g)+\frac{3}{2} \mathrm{H}_{2}(g)\) d. \(2 \mathrm{~N}_{2}(g)+6 \mathrm{H}_{2}(g) \rightleftharpoons 4 \mathrm{NH}_{3}(g)\)

Problem 28

At a particular temperature a \(2.00-\mathrm{L}\) flask at equilibrium contains \(2.80 \times 10^{-4}\) mole of \(\mathrm{N}_{2}, 2.50 \times 10^{-5}\) mole of \(\mathrm{O}_{2}\), and \(2.00 \times 10^{-2}\) mole of \(\mathrm{N}_{2} \mathrm{O}\). Calculate \(K\) at this temperature for the reaction $$ 2 \mathrm{~N}_{2}(g)+\mathrm{O}_{2}(g) \rightleftharpoons 2 \mathrm{~N}_{2} \mathrm{O}(g) $$ If \(\left[\mathrm{N}_{2}\right]=2.00 \times 10^{-4} M,\left[\mathrm{~N}_{2} \mathrm{O}\right]=0.200 M\), and \(\left[\underline{ \left.\mathrm{O}_{2}\right]}=\right.\) \(0.00245 M\), does this represent a system at equilibrium?

Problem 34

Write expressions for \(K_{\mathrm{p}}\) for the following reactions. a. \(2 \mathrm{Fe}(s)+\frac{3}{2} \mathrm{O}_{2}(g) \rightleftharpoons \mathrm{Fe}_{2} \mathrm{O}_{3}(s)\) b. \(\mathrm{CO}_{2}(g)+\mathrm{MgO}(s) \rightleftharpoons \mathrm{MgCO}_{3}(s)\) c. \(\mathrm{C}(s)+\mathrm{H}_{2} \mathrm{O}(g) \rightleftharpoons \mathrm{CO}(g)+\mathrm{H}_{2}(g)\) d. \(4 \mathrm{KO}_{2}(s)+2 \mathrm{H}_{2} \mathrm{O}(g) \rightleftharpoons 4 \mathrm{KOH}(s)+3 \mathrm{O}_{2}(g)\)

Problem 41

At \(900^{\circ} \mathrm{C}, K_{\mathrm{p}}=1.04\) for the reaction $$ \mathrm{CaCO}_{3}(s) \rightleftharpoons \mathrm{CaO}(s)+\mathrm{CO}_{2}(g) $$ At a low temperature, dry ice (solid \(\mathrm{CO}_{2}\) ), calcium oxide, and calcium carbonate are introduced into a \(50.0-\mathrm{L}\) reaction chamber. The temperature is raised to \(900^{\circ} \mathrm{C}\), resulting in the dry ice converting to gaseous \(\mathrm{CO}_{2}\). For the following mixtures, will the initial amount of calcium oxide increase, decrease, or remain the same as the system moves toward equilibrium at \(900^{\circ} \mathrm{C} ?\) a. \(655 \mathrm{~g} \mathrm{CaCO}_{3}, 95.0 \mathrm{~g} \mathrm{CaO}, P_{\mathrm{CO}_{2}}=2.55 \mathrm{~atm}\) b. \(780 \mathrm{~g} \mathrm{CaCO}_{3}, 1.00 \mathrm{~g} \mathrm{CaO}, P_{\mathrm{CO}_{2}}=1.04 \mathrm{~atm}\) c. \(0.14 \mathrm{~g} \mathrm{CaCO}_{3}, 5000 \mathrm{~g} \mathrm{CaO}, P_{\mathrm{CO}_{2}}=1.04 \mathrm{~atm}\) d. \(715 \mathrm{~g} \mathrm{CaCO}_{3}, 813 \mathrm{~g} \mathrm{CaO}, P_{\mathrm{CO}_{2}}=0.211 \mathrm{~atm}\)

Problem 42

Ethyl acetate is synthesized in a nonreacting solvent (not water) according to the following reaction: \(\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{H}+\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{OH} \rightleftharpoons \mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{C}_{2} \mathrm{H}_{5}+\mathrm{H}_{2} \mathrm{O} \quad K=2.2\) \(\begin{array}{ll}\text { Acetic acid } \text { Ethanol } & \text { Ethyl acetate }\end{array}\) For the following mixtures \((a-d)\), will the concentration of \(\mathrm{H}_{2} \mathrm{O}\) increase, decrease, or remain the same as equilibrium is established? a. \(\left[\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{C}_{2} \mathrm{H}_{5}\right]=0.22 \mathrm{M},\left[\mathrm{H}_{2} \mathrm{O}\right]=0.10 \mathrm{M}\), \(\left[\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{H}\right]=0.010 \mathrm{M},\left[\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{OH}\right]=0.010 \mathrm{M}\) b. \(\left[\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{C}_{2} \mathrm{H}_{5}\right]=0.22 \mathrm{M},\left[\mathrm{H}_{2} \mathrm{O}\right]=0.0020 \mathrm{M}\), \(\left[\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{H}\right]=0.0020 \mathrm{M},\left[\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{OH}\right]=0.10 \mathrm{M}\) c. \(\left[\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{C}_{2} \mathrm{H}_{5}\right]=0.88 M,\left[\mathrm{H}_{2} \mathrm{O}\right]=0.12 \mathrm{M}\), \(\left[\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{H}\right]=0.044 M,\left[\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{OH}\right]=6.0 \mathrm{M}\) d. \(\left[\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{C}_{2} \mathrm{H}_{5}\right]=4.4 M,\left[\mathrm{H}_{2} \mathrm{O}\right]=4.4 M\), \(\left[\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{H}\right]=0.88 \mathrm{M},\left[\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{OH}\right]=10.0 \mathrm{M}\) e. What must the concentration of water be for a mixture with \(\left[\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{C}_{2} \mathrm{H}_{5}\right]=2.0 \mathrm{M},\left[\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{H}\right]=0.10 M\), and \(\left[\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{OH}\right]=5.0 M\) to be at equilibrium? f. Why is water included in the equilibrium expression for this reaction?

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