- Indicate whether ΔG increases, decreases, or does not change when the partial pressure of H₂ is increased in each of the following reactions: (a) N₂(g) + 3 H₂(g) ⇌ 2 NH₃(g) (b) 2 HBr(g) ⇌ H₂(g) + Br₂(g) (c) 2 H₂(g) + C₂H₂(g) ⇌ C₂H₆(g)
Problem 76
Problem 77
Consider the reaction 2 NO2(g) → N2O4(g). (a) Using data from Appendix C, calculate ΔG° at 298 K. (b) Calculate ΔG at 298 K if the partial pressures of NO2 and N2O4 are 0.40 atm and 1.60 atm, respectively.
Problem 78a
Consider the reaction 3 CH4(g) → C3H8(g) + 2 H2(g). (a) Using data from Appendix C, calculate ΔG° at 298 K.
Problem 78b
Consider the reaction 3 CH4(g) → C3H8(g) + 2 H2(g). (b) Calculate ΔG at 298 K if the reaction mixture consists of 40.0 atm of CH4, 0.0100 atm of C3H8(g), and 0.0180 atm of H2.
- Use data from Appendix C to calculate the equilibrium constant, K, and ΔG° at 298 K for each of the following reactions: (a) H2(g) + I2(g) ⇌ 2 HI(g) (b) C2H5OH(g) ⇌ C2H4(g) + H2O(g) (c) 3 C2H2(g) ⇌ C6H6(g)
Problem 79
Problem 81a
Consider the decomposition of barium carbonate: BaCO3(s) ⇌ BaO(s) + CO2(g) Using data from Appendix C, calculate the equilibrium pressure of CO2 at (a) 298 K.
Problem 81b
Consider the decomposition of barium carbonate: BaCO3(s) ⇌ BaO(s) + CO2(g) Using data from Appendix C, calculate the equilibrium pressure of CO2 at (b) 1100 K.
Problem 83a
The value of Ka for nitrous acid (HNO2) at 25 °C is given in Appendix D. (a) Write the chemical equation for the equilibrium that corresponds to Ka.
Problem 83b
The value of Ka for nitrous acid (HNO2) at 25 °C is given in Appendix D. (b) By using the value of Ka, calculate ΔG° for the dissociation of nitrous acid in aqueous solution.
Problem 83c
The value of Ka for nitrous acid (HNO2) at 25 °C is given in Appendix D. (c) What is the value of ΔG at equilibrium?
Problem 83d
The value of Ka for nitrous acid (HNO2) at 25 °C is given in Appendix D. (d) What is the value of ΔG when [H+] = 5.0⨉10-2 M, [NO2-] = 6.0⨉10-4 M, and [HNO2] = 0.20 M?
Problem 84a
The Kb for methylamine (CH3NH2) at 25 °C is given in Appendix D. (a) Write the chemical equation for the equilibrium that corresponds to Kb.
Problem 84d
The Kb for methylamine (CH3NH2) at 25 °C is given in Appendix D. (d) What is the value of ΔG when [H+] = 6.7 × 10-9 M, [CH3NH3+] = 2.4 × 10-3 M, and [CH3NH2] = 0.098 M?
- (c) How many reversible paths are there between two states of a system?
Problem 85
Problem 85a
(a) Which of the thermodynamic quantities T, E, q, w, and S are state functions? (b) Which depend on the path taken from one state to another?
Problem 85d
(d) For a reversible isothermal process, write an expression for ΔE in terms of q and w and an expression for ΔS in terms of q and T.
Problem 86a
The crystalline hydrate Cd(NO3)2⋅4 H2O(s) loses water when placed in a large, closed, dry vessel at room temperature: Cd(NO3)2⋅4 H2O(s) → Cd(NO3)2(s) + 4 H2O(g) This process is spontaneous and ΔH° is positive at room temperature.
(a) What is the sign of ΔS° at room temperature?
Problem 86b
The crystalline hydrate Cd(NO3)2⋅4 H2O(s) loses water when placed in a large, closed, dry vessel at room temperature: Cd(NO3)2⋅4 H2O(s) → Cd(NO3)2(s) + 4 H2O(g) This process is spontaneous and ΔH° is positive at room temperature.
(b) If the hydrated compound is placed in a large, closed vessel that already contains a large amount of water vapor, does ΔS° change for this reaction at room temperature?
- Indicate whether each of the following statements is true or false. If it is false, correct it. (a) The feasibility of manufacturing NH3 from N2 and H2 depends entirely on the value of ΔH for the process N2(g) + 3 H2(g) → 2 NH3(g). (e) Spontaneous processes are those that are exothermic and that lead to a higher degree of order in the system.
Problem 87
Problem 88
For each of the following processes, indicate whether the signs of ΔS and ΔH are expected to be positive, negative, or about zero. (a) A solid sublimes. (b) The temperature of a sample of Co(s) is lowered from 60 °C to 25 °C. (c) Ethyl alcohol evaporates from a beaker. (d) A diatomic molecule dissociates into atoms. (e) A piece of charcoal is combusted to form CO2(g) and H2O(g).
- Ammonium nitrate dissolves spontaneously and endothermally in water at room temperature. What can you deduce about the sign of ΔS for this dissolution process?
Problem 91
Problem 92c
A standard air conditioner involves a refrigerant that is typically now a fluorinated hydrocarbon, such as CH2F2. An air-conditioner refrigerant has the property that it readily vaporizes at atmospheric pressure and is easily compressed to its liquid phase under increased pressure. The operation of an air conditioner can be thought of as a closed system made up of the refrigerant going through the two stages shown here (the air circulation is not shown in this diagram).
During expansion, the liquid refrigerant is released into an expansion chamber at low pressure, where it vaporizes. The vapor then undergoes compression at high pressure back to its liquid phase in a compression chamber. (c) In a central air-conditioning system, one chamber is inside the home and the other is outside. Which chamber is where, and why?
Problem 93b
Trouton’s rule states that for many liquids at their normal boiling points, the standard molar entropy of vaporization is about 88 J/mol‐K. b. Look up the normal boiling point of Br2 in a chemistry handbook or at the WebElements website (www.webelements.com) and compare it to your calculation. What are the possible sources of error, or incorrect assumptions, in the calculation?
- (a) Write the chemical equations that correspond to ΔG°f for NH3(g) and for CO(g). (b) For which of these formation reactions will the value of ΔG°f be more positive (less negative) than ΔH°f?
Problem 94
Problem 94c
(c) In general, under which condition is ΔG°f more positive (less negative) than ΔH°f ? (i) When the temperature is high, (ii) when the reaction is reversible, (iii) when ΔS°f is negative.
Problem 95a
Consider the following three reactions: (i) Ti(s) + 2 Cl2(g) → TiCl4(1g) (a) For each of the reactions, use data in Appendix C to calculate ΔH°, ΔG°, K, and ΔS ° at 25 °C.
Problem 95b
Consider the following three reactions: (i) Ti(s) + 2 Cl2(g) → TiCl4(1g) (ii) C2H6(g) + 7 Cl2(g) → 2 CCl4(g) + 6 HCl(g) (iii) BaO(s) + CO2(g) → BaCO3(s) (b) Which of these reactions are spontaneous under standard conditions at 25 °C?
Problem 95c
Consider the following three reactions: (i) Ti(s) + 2 Cl2(g) → TiCl4(1g) (ii) C2H6(g) + 7 Cl2(g) → 2 CCl4(g) + 6 HCl(g) (iii) BaO(s) + CO2(g) → BaCO3(s) (c) For each of the reactions, predict the manner in which the change in free energy varies with an increase in temperature.
Problem 96
Using the data in Appendix C and given the pressures listed, calculate Kp and ΔG for each of the following reactions:
(a) N2(g) + 3 H2(g) → 2 NH3(g) PN2 = 2.6 atm, PH2 = 5.9 atm, PNH3 = 1.2 atm
(b) 2 N2H4(g) + 2 NO2(g) → 3 N2(g) + 4 H2O(g) PN2H4 = PNO2 = 5.0 × 10-2 atm, PN2 = 0.5 atm, PH2O = 0.3 atm
(c) N2H4(g) → N2(g) + 2 H2(g) PN2H4 = 0.5 atm, PN2 = 1.5 atm, PH2 = 2.5 atm
Problem 97a
(a) For each of the following reactions, predict the sign of ΔH° and ΔS° without doing any calculations. (i) 2 Mg(s) + O2 (g) ⇌ 2 MgO(s) (ii) 2 KI(s) ⇌ 2 K(g) + I2(g) (iii) Na2(g) ⇌ 2 Na(g) (iv) 2 V2O5(s) ⇌ 4 V(s) + 5 O2(g)
Ch.19 - Chemical Thermodynamics
