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Chapter 7
Energy, Rate, and Equilibrium
Solutions to the Even-Numbered Problems
7.2 a. Exothermic. H˚ is negative, meaning that energy is released by the reaction.
b. Endothermic. Energy is shown as a reactant in the reaction.
7.4 H2O(g) has a greater entropy than H2O(l). Gases have a greater degree of disorder than
liquids.
7.6 G = H - TS
substituting signs: G = (+) – T
Depending on the magnitude of T, the result can be positive or negative. Hence, the
process is temperature dependent.
4.18 J
7.8 7.0 x 102 cal x = 2.9 x 103 J
1 cal
7.10 Net energy is the difference in energy between products and reactants. Activation energy
is the threshold energy that must be overcome in order to cause a chemical reaction.
7.12 The rate of chemical reactions critical to the growth process decreases at the lower
temperature of the refrigerator.
7.14 An increase in the rate of the forward reaction favors product formation.
7.16 No. The equilibrium process is dynamic; products and reactants continuously
interconvert at the same rate.
7.18 The equilibrium favors reactants. A very low value for the equilibrium constant indicates
that the ratio of products to reactants is very low. Therefore reactant concentration is
larger than product concentration.
61
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7.24 Often, decomposition reactions are endothermic because energy is required to break
bonds in the reactant in order to produce the products. On the other hand, combination
reactions are often exothermic because bonds are formed, releasing energy.
7.28 Fuel value is a measure of the amount of energy per gram of food. Food whose energy is
not used to maintain normal body temperature or in muscular activity is stored as fat,
contributing to obesity.
7.30 The specific heat of a substance is the number of calories of heat needed to raise the
temperature of one gram of the substance one degree Celsius.
7.32 The second law of thermodynamics states that the universe spontaneously tends toward
increasing disorder or randomness.
1.14 x 103 calories are derived from 0.0500 moles of the nutrient substance.
7.40 a. Entropy increases. Conversion of a single solid object, the log, into carbon monoxide,
carbon dioxide, and water (all gases) and ashes (disordered solid) increases the
disorder of the substance.
7.42 G = H – TS
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Depending on the magnitude of T, the result can be positive or negative. Hence, the
process is temperature dependent.
7.44 Energy is released when chemical bonds form. The bond energy is defined as the energy
released when a chemical bond is formed.
7.48 The activation energy is the threshold energy barrier that must be overcome to cause a
chemical reaction to take place.
7.54 Our example is lactase. Lactase is the enzyme critical to the digestion of lactose, a milk
sugar. Lactose intolerance is a problem for perhaps 20% of the population; digestion of
lactose is impeded by the inability of the body to make the enzyme lactase.
7.56 Figure 7.2(b) in the textbook depicts a generalized endothermic reaction. The presence of
a catalyst would lower the activation energy (similar to the effect shown in Figure 7.11 in
the textbook, illustrated for an exothermic reaction) and would leave the initial and final
energies unchanged. Consequently, the change in enthalpy would remain the same.
7.58 The rate equation for the reaction is determined to be rate = k[H2O2].
It is known that the value of k=3.1 x 10-3 s-1. We are not given specific values for the
[H2O2], so we will start with [H2O2] = 1 M and determine the rate.
To determine the effect of doubling the concentration of H2O2, we use [H2O2] = 2 M and
determine the rate.
Comparing the rates obtained, it can be concluded that doubling the concentration of
H2O2 will cause the rate of the reaction to double.
7.60 An increase in the temperature of reactants increases the rate of a reaction for two
reasons:
• The speed of reactant molecules increases as the temperature increases. Faster-
moving molecules collide more frequently, increasing the probability of reaction.
• Reactant molecules have more kinetic energy at higher temperatures; thus, a greater
fraction of all collisions will be effective collisions.
63
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7.62 Rate = k[H2S]n[Cl2]n Note: n and n must be experimentally determined.
7.64 The catalyst is involved in the formation of the activated complex, an unstable
intermediate in the reaction. When the complex breaks apart to form products, the
catalyst is regenerated; it is free to repeat the process over and over again.
7.68 a. Increasing the temperature of this endothermic reaction will cause the equilibrium
position to shift to the right and produce more of product B. Therefore, diagram (C)
represents the system once equilibrium is reestablished.
b. Decreasing the temperature of this endothermic reaction will cause the equilibrium
position to shift to the left and produce more of reactant A. Therefore, diagram (B)
represents the system once equilibrium is reestablished.
7.70 Le Chatelier’s principle allows us to predict conditions of temperature, pressure, etc., that
will favor the production of products.
7.72 The rates of the forward and reverse reactions are equal for a reaction at equilibrium.
7.74 A catalyst increases the rates of forward and reverse reactions to the same extent. We
may reach equilibrium faster, but the equilibrium position will be the same as would be
achieved without the catalyst.
7.76 Gaseous
[HCl]2
7.78 K eq =
[H2S][Cl2 ]
7.80 The rate constant is a measure of how rapidly a reaction reaches equilibrium or
completion.
The equilibrium constant describes the ratio of product and reactant concentrations at
equilibrium. It is a measure of the completeness of the reaction.
[NH3 ]2
7.82 Keq =
[N 2 ][H 2 ]3
[1.8 x 10 -4 ]2
Keq =
[0.071][9.2 x 10 -3 ]3
3.2 x 10 -8
Keq = = 0.585 0.59
[0.071][7.8 x 10 -7 ]
64
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[H 2 S] 2
7.84 Keq =
[S 2 ][H 2 ] 2
[7.3 x 10 -1 ]2
Keq =
[1.1 x 10 -6 ][2.1 x 10 1 ]2
[H 2 S] 2
7.86 Keq =
[S 2 ][H 2 ] 2
Rearrange to solve for [H2S]2
Substitute,
7.88 a. Equilibrium shifts to the right. Increasing the temperature provides more energy to
drive the endothermic reaction to the right.
b. Equilibrium shifts to the left. An increase in pressure will favor the direction that
favors a smaller volume: Three moles of gaseous product will convert to two moles of
gaseous reactant.
c. No change in equilibrium position. The catalyst has no effect on equilibrium
position.
7.92 a. Adding more carbon has no effect on the equilibrium because carbon is a solid.
Solids and pure liquids are not a part of the equilibrium expression.
b. Adding more H2 shifts the equilibrium to the right, favoring the formation of
methane.
65
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c. Removing CH4 shifts the equilibrium to the right.
d. Increasing the temperature shifts the equilibrium to the left. Increasing the
temperature increases heat energy and heat is viewed as a product.
e. Addition of a catalyst has no effect on the equilibrium position.
7.94 Since the total moles of reactants in the gaseous state is equal to the total moles of
products in the gaseous state, an increase in pressure will have no effect on the
concentration of NO(g).
[NO]2
7.96 K eq =
[N2 ][O2 ]
7.98 True. In an endothermic reaction, heat energy is absorbed from the surroundings; heat
can be viewed as a reactant. Adding reactant shifts the equilibrium to the right.
7.100 Heating shifts the equilibrium to the right as well. Gases are less soluble at elevated
temperatures (Henry’s Law) and the beverage goes “flat”.
[CO][H 2 ]
7.102 The solid, C, is not written into the equilibrium expression. Keq =
[H 2 O]
[CO][H 2 ] [0.40][0.20]
7.104 Keq = = = 0.20 or 2.0 x 10-1
[H 2 O] [0.40]
7.106 According to the reaction equation, C(s) + H2O(g) CO(g) + H2(g), experimental
conditions that would result in an increase of H2(g) include adding H2O(g), removing
CO(g), or decreasing the pressure.
66
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