4. Using the data from Handout 5, what is the standard enthalpy of formation of N 2 O (g)? What does this mean?

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1 EXTRA HOMEWORK 3A 1. In each of the following pairs, tell which has the higher entropy. (a) One mole of ice or one mole of liquid water (b) One mole of liquid propane or one mole of gaseous propane (c) One mole of gray tin (diamond-like structure) or one mole of white tin (metal-like structure) (d) One mole of solid magnesium nitrate or one mole of aqueous magnesium nitrate 2. Will the entropy change of each of the following processes be positive or negative, and will the disorder in each process increase or decrease? (a) One mole of solid aluminum melting to one mole of molten aluminum. (b) One mole of iodine vapor deposing to one mole of solid iodine (c) One mole of dissolved sodium acetate crystallizing out of an aqueous solution (d) One mole of dissolved carbon dioxide bubbling out of a soda 3. Predict the sign of the entropy change in each of the following reactions. (a) BaCO 3 (s) BaO (s) + CO 2 (g) (b) Mg (s) + Cl 2 (g) MgCl 2 (s) (c) CH 4 (g) + 2O 2 (g) 2CO 2 (g) + 2H 2 O (l) (d) Ni 3 (PO 4 ) 2 (s) 3Ni 2+ (aq) + 2PO 4 3- (aq) (e) 2H + (aq) + SO 3 2- (aq) H 2 O (l) + SO 2 (g) (f) Br 2 (l) + Cl 2 (g) 2BrCl (l) 4. Using the data from Handout 5, what is the standard enthalpy of formation of N 2 O (g)? What does this mean? 5. Using the data from Handout 5, what is the standard absolute entropy of N 2 O (g)? What does this mean? 6. Using data from the appendix, calculate the standard change in entropy, ΔSº, for the following reactions. (a) 2S (s, monoclinic) + 3O 2 (g) 2SO 3 (g) (b) C 3 H 8 (g) + 5O 2 (g) 3CO 2 (g) + 4H 2 O (g)

2 EXTRA HOMEWORK 3B 1. For the allotropic phase change of phosphorus at 298 K: P (s) (white) P (s) (red) (a) Using data from Handout 5, calculate the standard change in enthalpy for the allotropic phase change (b) Using data from Handout 5, calculate the standard change in entropy for the allotropic phase change (c) Calculate the standard change in entropy of the surroundings for the allotropic phase change (d) Calculate the standard change in entropy of the universe for the allotropic phase change (e) Is the forward or reverse allotropic phase change spontaneous at 298 K? 2. Predict whether each of the following processes will be spontaneous, nonspontaneous, or it cannot be determined. (a) H = + and S = + (b) H = + and S = (c) H = and S = + (d) H = and S = 3. Using the data from Handout 5, what is the standard free energy of formation of N 2 O (g)? What does this mean? 4. For the reaction at 298 K Fe 2 O 3 (s) + 3H 2 (g) 2Fe (s) + 3H 2 O (g) use data from Handout 5 to answer the following. (a) Calculate ΔHº (b) Calculate ΔSº (c) Calculate ΔGº (d) Calculate ΔGº from ΔGº = ΔHº - T ΔSº (e) Is the reaction spontaneous under standard conditions at 298 K? (f) Do the enthalpy change and the entropy change work for or against spontaneity? (g) At a temperature higher than 298 K, would the forward reaction be more or less spontaneous? 5. For the phase change: C 6 H 6 (l) C 6 H 6 (g) Hº = 33.9 kj and Sº = 96.4 J/K. (a) Calculate the standard free energy change, ΔGº, for the reaction at 293 K, and tell if the forward or reverse reaction is spontaneous at this temperature (b) Calculate the standard free energy change, ΔGº, for the reaction at 353 K, and tell if the forward or reverse reaction is spontaneous at this temperature (c) Calculate the boiling point of liquid benzene

3 EXTRA HOMEWORK 3C 1. For the reaction: 2NO 2 (g) N 2 O 4 (g) use data from Handout 5 to answer the following. (a) Calculate ΔGº at 298 K for the forward reaction. (b) If the pressures of the gases are p NO2 = 0.29 atm and p N2O4 = 1.6 atm, calculate ΔG at 298 K, and predict the direction the reaction will shift to reach equilibrium. (c) If the pressures of the gases are p NO2 = 0.21 atm and p N2O4 = 0.50 atm, calculate ΔG at 298 K, and predict the direction the reaction will shift to reach equilibrium. (d) If the pressures of the gases are p NO2 = 1.0 atm and p N2O4 = 1.0 atm, calculate ΔG at 298 K, and predict the direction the reaction will shift to reach equilibrium. 2. For the reaction 3H 2 (g) + N 2 (g) 2NH 3 (g) use data from Handout 5 to answer the following. (a) Calculate ΔGº at 298 K for the forward reaction. (b) Is the forward reaction spontaneous under standard conditions? (c) Predict whether the equilibrium constant be > 1 or < 1 at 298 K. (d) Calculate K eq at 298 K (e) Does the K eq favor reactants or products? (f) What effect would an increase in pressure have on the spontaneity of the reaction? 3. For the combustion of liquid methanol: C 2 H 5 OH (l) + 3O 2 (g) 2CO 2 (g) + 3H 2 O (l) (a) Calculate ΔGº (b) Is the reaction spontaneous under standard conditions? (c) Predict whether the equilibrium constant be > 1 or < 1 at 298 K (d) Calculate K eq at 298 K (e) Does the K eq favor reactants or products? (f) What effect would an increase in temperature have on the spontaneity of the reaction? (g) What effect would an increase in pressure have on the spontaneity of the reaction? (continued on next page)

4 4. Nitrous acid ionizes according to the following equation: HNO 2 (aq) H + (aq) + NO 2 - (aq) At 298 K the ΔG f for nitrous acid is kj/mol, and the ΔG f for the nitrite ion is kj/mol. (a) Calculate the standard free energy change of the reaction at 298 K. (b) Is the reaction spontaneous under standard conditions? (c) Predict whether the K a of nitrous acid will be > 1 or < 1 at 298 K. (d) From the standard free energy change of the reaction, calculate the K a of acetic acid at 298 K. (e) How does your calculated K a compare with the value found on Handout 3? (f) If the concentrations of each species in solution are [HNO 2 ] = 0.100M, [H + ] = 1.00 x 10-3 M, and [NO 2 - ] = 1.00 x 10-3 M, calculate ΔG at 298 K. (g) Is the reaction spontaneous under the conditions in (f)? 5. Benzoic acid (C 6 H 5 CO 2 H) is a weak organic acid with K a = 6.5 x 10-5 at 298 K. (a) Write the equilibrium constant expression for the ionization of benzoic acid in water. (b) What is molarity of the benzoate ion, C 6 H 5 CO 2 - ion in a 1.00 M solution of benzoic acid in water? (c) What is the ph of the solution? (d) Predict whether ΔG for the reaction in (a) will be > 0 or < 0 at 298 K. (e) What is the standard free energy change of the ionization of benzoic acid in water? 6. The solubility of tin (II) fluoride in water is g/l at 20.ºC and g/l at 80. C. (a) Calculate the K sp for tin (II) fluoride at each temperature. (b) Determine the heat of solution and the entropy change of solution of tin (II) fluoride by using a van t Hoff plot.

5 EXTRA HOMEWORK 3D 1. Assuming the concentrations of 1 M for all of the following solutions, use standard reduction potentials found in Table 18.1 to determine which of the following reactions are spontaneous. (a) Ba (s) + Fe 2+ (aq) Ba 2+ (aq) + Fe (s) (b) 2Au (s) + 3Br 2 (l) 2Au 3+ (aq) + 6Br - (aq) (c) H 2 SO 3 (aq) + H 2 O (l) + Pb 2+ (aq) SO 4 2- (aq) + 4H + (aq) + Pb (s) (d) Cd (s) + 2H + (aq) Cd 2+ (aq) + H 2 (g) 2. Consider a standard cell composed of a Zn Zn 2+ (1 M) half-cell and a Sn Sn 2+ (1 M) half-cell (a) Determine the spontaneous chemical reaction that takes place in this cell, assuming that the line notation may be written incorrectly (b) What is Ɛº for the cell? (c) Which metal, Zn or Sn, will be the anode, and which metal will be the cathode? (d) Do the electrons flow from Zn to Sn in the external circuit, or the other way? (e) What is the shorthand line notation for this cell? 3. Consider a standard cell composed of a Ba Ba 2+ (1 M) half-cell and a Cr Cr 3+ (1 M) half-cell (a) Write the spontaneous chemical reaction that takes place in this cell (b) What is Ɛº for the cell? (c) Which metal, Ba or Cr, will be the cathode, and which metal will be the anode? (d) Do the electrons flow from Ba to Cr in the external circuit, or the other way? (e) What is the shorthand line notation for this cell? 4. Find the missing standard reduction potentials for these following half reactions on Handout 5: MnO 2 (s) + 4H + (aq) + 2e - Mn 2+ (aq) + 2H 2 O (l) Ɛ = V Ag + (aq) + e - Ag (s) Ɛ = V I 2 (s) + 2e - 2I - (aq) Ɛ = PbSO 4 (s) + 2e - Pb (s) + SO 2-4 (aq) Ɛ = 2H + (aq) + VO + 2 (aq) + e- VO 2+ (aq) + H 2 O (l) Ɛ = Assuming all reactants and products are at unit activity, (a) What substance from above is the best oxidizing agent and what is the best reducing agent? (b) Will manganese (IV) oxide oxidize metallic silver? (c) Will metallic silver reduce solid iodine? (d) Will VO 2 + oxidize manganese (II) ions to manganese (IV) oxide? (e) Will metallic lead in a sulfate solution reduce solid iodine? (f) Will silver ions oxidize VO 2+? (g) Will manganese (IV) oxide oxidize iodide ions?

6 EXTRA HOMEWORK 3E 1. Consider the cell Mn (s) Mn 2+ (0.10 M) Fe 2+ (1.0 M) Fe (s) (a) Write the spontaneous chemical reaction that takes place in this cell (b) Which metal, Mn or Fe, will be the anode, and which metal will be the cathode? (c) What is Ɛº for the cell? (d) What is Ɛ for the cell at 298 K with the concentrations specified above? 2. A silver-magnesium battery is set up under standard conditions with all species at unit activity. Initially, the voltage developed by this cell is 3.17 V. As the battery is used, the concentration of the silver ion gradually decreases, and that of the magnesium ion increases. (a) Calculate the ratio of activities of products to reactants, Q, when the cell voltage is 3.00 V at 298 K. (b) Calculate the ratio of activities of products to reactants, Q, when the cell voltage is 0.00 V at 298 K. 3. Consider the cell Mg (s) Mg 2+ ( M) Ag + ( M) Ag (s) for which Ɛº = 3.17 V. Does the cell voltage increase, decrease, or remain the same when each of the following changes is made? (a) The given magnesium electrode is replaced by a larger magnesium electrode. (b) Excess 1.0 M sodium hydroxide is added to the anode compartment (c) Excess 1.0 M ammonia is added is added to the cathode compartment. 4. Find the standard reduction potentials for these following half reactions from Table 18.1: 2- SO 4 (aq) + 4H + (aq) + 2e - H 2 SO 3 (aq) + H 2 O (l) Ɛ = Ag + (aq) + e - Ag (s) Ɛ = Assuming all reactants and products are at unit activity, (a) Write the balanced overall reaction for a successful cell made from these two couples. (b) What is Ɛ for the cell? (c) What is the equilibrium constant for the reaction at 25 C? (d) Calculate the ratio of activities of products to reactants, Q, which will produce a cell voltage of 0.51 V at 25 C? 5. A standard cell at 298 K is composed of a Mg Mg 2+ (1 M) half-cell and a Ni Ni 2+ (1 M) half-cell. (a) Determine the spontaneous chemical reaction that takes place in this cell. (b) What is Ɛ º for the cell? (d) If the Ni 2+ concentration drops to 0.50 M and is maintained there, calculate the concentration of Mg 2+ ions in the cell when the voltage is 2.10 V. (continued on next page)

7 5. Consider a standard cell composed of an Au Au 3+ (1 M) half-cell and a Ag Ag + (1 M) half-cell. (a) Determine the spontaneous chemical reaction that takes place in this cell. (a) What is Ɛº for the cell at 298 K? (c) Calculate the voltage of a different cell at 298 K when [Au 3+ ] = M and [Ag + ] = M (d) Calculate the voltage of the cell in (c) when 10.% of the Au 3+ has reacted away. (e) Calculate the voltage of the cell in (c) when 50.% of the Au 3+ has reacted away. (f) Calculate the voltage of the cell in (c) when 99% of the Au 3+ has reacted away. EXTRA HOMEWORK 3F 1. Give the electrolysis products at the anode and cathode for each of the following liquids or solutions. (a) KCl (l) (b) KCl (aq) (c) AuCl 3 (l) (d) AuCl 3 (aq) (a) KNO 3 (aq) (b) Au(NO 3 ) 3 (aq) (c) HCl (aq) (h) HNO 3 (aq) 2. Give the anode and cathode half-reactions that take place in questions 1a and 1b. 3. How many grams of metallic magnesium can be obtained by passing a current of 5.00 A through molten magnesium chloride for 3.00 hours? 4. Electricity is passed through an aluminum nitrate solution for 45 minutes, depositing g of aluminum on the cathode. How many amperes was the current? 5. An aqueous solution of gold (III) nitrate is electrolyzed by passing a current of 10.0 A through an electrolysis cell for a certain length of time. In this process 12.5 g of gold are deposited on the cathode. (a) What is the half-reaction that occurs at the cathode? (b) What is the half-reaction that occurs at the anode? (c) How long does the process take? (d) What mass of oxygen gas is liberated at the anode? EXTRA 3A ANSWERS 1. (a) liquid water (b) gaseous propane (c) white tin (d) aqueous Mg(NO 3 ) 2 2. (a) +, increase (b) -, decrease (c) -, decrease (d) +, increase 3. (a) positive (b) negative (c) negative (d) positive (e) positive (f) negative kj/mol; the change in enthalpy (or the amount of heat absorbed) when one mole of NO 2 (g) is formed under standard conditions via the following reaction: ½N 2 (g) + O 2 (g) N 2 O (g) J/molK; the amount of entropy (or disorder) contained in one mole of NO 2 (g) under standard conditions 6. (a) -167 J/K (b) 103 J/K

8 EXTRA 3B ANSWERS 1. (a) -18 kj (b) -18 J/K (c) 60. J/K (d) 42 J/K (e) forward 2. (a) can t be determined (b) nonspontaneous (c) spontaneous (d) can t be determined kj/mol; the change in Gibbs free energy (or the amount of energy available for work, or the direction of spontaneity) for the reaction: ½N 2 (g) + O 2 (g) N 2 O (g) when a reaction vessel contains one-half mole of N 2 (g), one mole of O 2 (g), and one mole of NO 2 (g) under standard conditions 4. (a) 100. kj (b) 138 J/K (c) 53 kj (d) 59 kj ( 53 kj) (e) no (f) H against, S for (g) more 5. (a) 5.6 kj, reverse (b) -0.1 kj, forward (c) 352 K = 78ºC EXTRA 3C ANSWERS 1. (a) -6 kj (b) 1 kj, no left (c) 0 kj, no shift (d) -6 kj, shift right 2. (a) -34 kj (b) yes (c) >1 (d) 9.1 x 10 5 (e) products (f) more spontaneous 3. (a) kj (b) yes (c) >1 (d) 8.49 x or e 534 (e) products (f) less spontaneous (g) more spontaneous 4. (a) 19.4 kj (b) no (c) <1 (d) 3.98 x 10-4 (e) almost identical: 3.98 x x 10-4 (f) -9.1 kj (g) yes 5. (a) K a = [H 3 O + ][C 6 H 5 CO - 2 ]/[C 6 H 5 CO 2 H] (b) 8.0 x 10-3 M (c) 2.10 (d) >0 (e) 24 kj 6. (a) 1.2 x 10-10, 8.4 x (b) 28 kj, -96 J/K EXTRA 3D ANSWERS 1. (a) spontaneous (b) nonspontaneous (c) nonspontaneous (d) spontaneous 2. (a) Zn + Sn 2+ Zn 2+ + Sn (b) 0.62 V (c) anode Zn, cathode Sn (d) Zn to Sn 3. (a) 3Ba + 2Cr 3+ 3Ba Cr (b) 2.17 V (c) anode Ba, cathode Cr (d) Ba to Cr 4. (a) MnO 2 ox. agent, Pb with SO 2-4 red. agent (b) yes (c) no (d) no (e) yes (f) no (g) yes

9 EXTRA 3E ANSWERS 1. (a) Mn + Fe 2+ Mn 2+ + Fe (b) Mn anode, Fe cathode (c) 0.74 V (d) 0.77 V 2. (a) 5.6 x 10 5 (b) 1.43 x or e (a) remain the same (b) increase (c) decrease 4. (a) H 2 SO 3 + H 2 O + 2Ag + SO H + + 2Ag (b) 0.60 V (c) 1.9 x (d) (a) Mg + Ni 2+ Mg 2+ + Ni (b) 2.14 V (c) 11 M 6. (a) 3Ag + Au 3+ 3Ag + + Au (b) 0.70 V (c) V (d) 0.73 V (e) 0.68 V (f) 0.63 V EXTRA 3F ANSWERS 1. (a) Cl 2 (g), K (s) (b) Cl 2 (g), H 2 (g) (c) Cl 2 (g), Au (s) (d) Cl 2 (g), Au (s) (d) O 2 (g), H 2 (g) (f) O 2 (g), Au (s) (g) Cl 2 (g), H 2 (g) (h) O 2 (g), H 2 (g) 2. (a) anode 2Cl - Cl 2 + 2e - cathode K + + e - K (b) anode 2Cl - Cl 2 + 2e - cathode 4H 2 O + 4e - 2H 2 + 4OH g A 5. (a) Au e - Au (b) 2H 2 O O 2 + 4e - + 4H + (c) 30.6 min (d) 1.52 g

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