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59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 Assigned questions for Lecture 8 are listed below (there are two sets). The questions occur in the following editions of “Physical Chemistry” by P.W. Atkins: 11th edition 10th edition 9th edition 8th edition Note: The letter “P” in front of a number indicates that the question is in the “Problem” category as opposed to the “Exercise” category in Atkins’ books. Updates are highlighted in yellow. This question set is a bit unusual in comparison to the previous sets in that the majority of these problems have disappeared from the 10th and 11th editions without explanation. Question 8.01 n/a n/a 2.6 2.6 Question is missing from the 10th edition. 2.6(a) (8th, 9th) A sample of 1.00 mol H2O(g) is condensed isothermally and reversibly to liquid water at 100°C. The standard enthalpy of vaporization of water at 100°C is 40.656 kJ mol−1. Find w, q, ΔU, and ΔH for this process. 2.6(b) (8th, 9th) A sample of 2.00 mol CH3OH(g) is condensed isothermally and reversibly to liquid at 64°C. The standard enthalpy of vaporization of methanol at 64°C is 35.3 kJ mol−1. Find w, q, ΔU, and ΔH for this process. Question 8.02 n/a n/a 2.16 2.16 Question is missing from the 10th edition. 2.16(a) (8th, 9th) A certain liquid has ΔvapH = 26.0 kJ mol-1. Calculate q, w, ΔH, and ΔU when 0.50 mol is vaporized at 250 K and 750 Torr. 2.16(b) (8th, 9th) A certain liquid has ΔvapH = 32.0 kJ mol-1 . Calculate q, w, ΔH, and ΔU when 0.75 mol is vaporized at 260 K and 765 Torr. University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 1 59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 Question 8.03 n/a n/a 2.17 20.21(b only) Question is missing from the 10th and 11th editions, and only the b-list question is given in the 8th edition for some reason. 2.17(a) (9th) Calculate the lattice enthalpy of SrI2 from the following data: 2.17(b) (8th, 9th) Calculate the lattice enthalpy of MgBr2 from the following data: Question 8.04 n/a n/a n/a n/a Old 7th edition question. (Ex. 2.31a, 7th Ed.) Calculate the standard enthalpy of hydrogenation of 1-hexene to hexane given that the standard enthalpy of combustion of 1-hexene is -4003 kJ mol-1. (Ex. 2.31b, 7th Ed.) Calculate the standard enthalpy of hydrogenation of 1-butene to butane given that the standard enthalpy of combustion of 1-butene is -2717 kJ mol-1. Question 8.05 2C.2 2C.2 2.18 2.17 2C.2(a) The standard enthalpy of formation of ethylbenzene is −12.5 kJ mol-1. Calculate its standard enthalpy of combustion. 2C.2(b) The standard enthalpy of formation of phenol is −165.0 kJ mol-1. Calculate its standard enthalpy of combustion. University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 2 59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 Question 8.06 P2C.3, P2C.4 2C.3 2.19 2.18 P2C.3(a) The standard enthalpy of combustion of cyclopropane is −2091 kJ mol-1 at 25°C. From this information and enthalpy of formation data for CO2(g) and H2O(g), calculate the enthalpy of formation of cyclopropane. The enthalpy of formation of propene is +20.42 kJ mol-1. Calculate the enthalpy of isomerization of cyclopropane to propene. P2C.4(b) From the following data, determine for diborane, B2H6(g), at 298 K: Question 8.07 2C.4 2C.5 2.2 2.19 2C.4(a) When 120 mg of naphthalene, C10H8(s), was burned in a bomb calorimeter the temperature rose by 3.05 K. Calculate the calorimeter constant. By how much will the temperature rise when 150 mg of phenol, C6H5OH(s), is burned in the calorimeter under the same conditions? 2C.4(b) When 225 mg of anthracene, C14H10(s), was burned in a bomb calorimeter the temperature rose by 1.75 K. Calculate the calorimeter constant. By how much will the temperature rise when 125 mg of phenol, C6H5OH(s), is burned in the calorimeter under the same conditions? Note: In the 8th/9th editions, the mass of anthracene is 2.25 mg. Question 8.08 n/a n/a 2.21 2.2 Question is missing from the 10th and 11th editions. 2.21(a) (9th), 2.22(a) (8th) Calculate the standard enthalpy of solution of AgCl(s) in water from the enthalpies of formation of the solid and the aqueous ions. 2.21(b) (9th), 2.22(b) (8th) Calculate the standard enthalpy of solution of AgBr(s) in water from the enthalpies of formation of the solid and the aqueous ions. Question 8.09 n/a n/a n/a n/a Old 7th edition question. (Ex. 2.39a, 7th Ed.) Use the standard enthalpies of formation to calculate the standard enthalpies of the following reactions: (a) 2NO2 (g) ⇌ N2O4 (g) (b) NH3 (g) + HCl (g) ⇌ NH4Cl (g) University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 3 59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 (Ex. 2.39b, 7th Ed.) Use the standard enthalpies of formation to calculate the standard enthalpies of the following reactions: (a) cyclopropane (g) ⇌ propene (g) (b) HCl (aq) + NaOH (aq) ⇌ NaCl(aq) + H2O (aq) Question 8.10 n/a n/a 2.22 2.21 Question is missing from the 10th edition. 2.22(a) (9th), 2.23 (8th) The standard enthalpy of decomposition of the yellow complex H3NSO2 into NH3 and SO2 is +40 kJ mol-1. Calculate the standard enthalpy of formation of H3NSO2. 2.22(a) (9th), 2.23 (8th) Given that the standard enthalpy of combustion of graphite is −393.51 kJ mol-1 and that of diamond is −395.41 kJ mol-1, calculate the enthalpy of the graphiteto-diamond transition. Question 8.11 n/a n/a 2.26 2.25 Question is missing from the 10th edition. 2.26(a) (9th), 2.25(a) (8th). Use the information in Table 2.2 (Appendix, 8th & 9th)/Table 2B.1 (Appendix 10th, 11th) to predict the standard reaction enthalpy of 2 NO2(g) → N2O4(g) at 100°C from its value at 25°C. Assume that the heat capacities are constant over this temperature range. 2.26(b) (9th), 2.25(b) (8th). Use the information in Table 2.2 (Appendix, 8th & 9th)/Table 2B.1 (Appendix 10th, 11th) to predict the standard reaction enthalpy of 2 H2(g) + O2(g) → 2 H2O(l) at 100°C from its value at 25°C. Assume that the heat capacities are not constant over this temperature range, and are parameterized as Cp,m = a + bT + c /T 2. Question 8.12 2C.7 2C.8 2.27 2.26 2C.7(a). From the data in the appendix tables, calculate ΔrH⊖ and ΔrU⊖ at (a) 298 K, (b) 478 K for the reaction C(graphite) + H2O(g) → CO(g) + H2(g). Assume all heat capacities to be constant over the temperature range of interest. Note: the temperature for (b) in the 10th edition is 378 K - not sure why they changed it. 2C.7(b). Calculate ΔrH⊖ and ΔrU⊖ at 298 K and ΔrH⊖ at 427 K for the hydrogenation of ethyne (acetylene) to ethene (ethylene) from the enthalpy of combustion and heat capacity data in the appendix tables. Assume the heat capacities to be constant over the temperature range involved. Note: In the 8th/9th editions the temperature is 348 K. University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 4 59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 Question 8.13 n/a n/a 2.28 2.27 2.28(a) (9th), 2.29(a) (8th). Calculate ΔrH⊖ for the reaction Zn(s) + CuSO4(aq) → ZnSO4(aq) + Cu(s) from the information in the appendix tables. 2.28(a) (9th), 2.29(a) (8th). Calculate ΔrH⊖ for the reaction NaCl(aq) + AgNO3(aq) → AgCl(s) + NaNO3(aq) from the information in the appendix tables. Question 8.14 n/a 2C.10 2.29 2.28 2C.10(a) Set up a thermodynamic cycle for determining the enthalpy of hydration of Mg2+ ions using the following data: enthalpy of sublimation of Mg(s), +167.2 kJ mol-1; first and second ionization enthalpies of Mg(g), 7.646 eV and 15.035 eV; dissociation enthalpy of Cl2(g), +241.6 kJ mol-1; electron gain enthalpy of Cl(g), −3.78 eV; enthalpy of solution of MgCl2(s), −150.5 kJ mol-1; enthalpy of hydration of Cl−(g), −383.7 kJ mol-1. 2C.10(b) Set up a thermodynamic cycle for determining the enthalpy of hydration of Ca2+ ions using the following data: enthalpy of sublimation of Ca(s), +178.2 kJ mol-1; first and second ionization enthalpies of Ca(g), 589.7 kJ mol-1 and 1145 kJ mol-1; enthalpy of vaporization of bromine, +30.91 kJ mol-1; dissociation enthalpy of Br2(g), +192.9 kJ mol-1; electron gain enthalpy of Br(g), −331.0 kJ mol-1; enthalpy of solution of CaBr2(s), −103.1 kJ mol-1; enthalpy of hydration of Br−(g), −289 kJ mol-1. Note: This question is missing from only the 11th edition. Not sure why! University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 5 59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 Solution 8.01 n/a n/a 2.6 2.6 University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 6 59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 Solution 8.02 n/a n/a 2.16 2.16 University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 7 59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 Solution 8.03 n/a n/a 2.17 20.21(b only) University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 8 59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 Solution 8.04 n/a n/a n/a n/a (Ex. 2.31b, 7th Ed.) University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 9 59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 Solution 8.08 n/a n/a 2.21 2.2 n/a n/a n/a Solution 8.09 n/a (Ex. 2.39b, 7th Ed.) ! University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 10 59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 Solution 8.10 n/a n/a 2.22 2.21 University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 11 59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 Solution 8.11 n/a n/a 2.26 2.25 University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 12 59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 Solution 8.13 n/a n/a 2.28 2.27 University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 13 59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 Solution 8.14 n/a 2C.10 2.29 2.28 University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 14 59-240 Physical Chemistry - Question Set #8 - Lecture 8 - v. 2.1 - updated Oct. 14, 2018 University of Windsor - Department of Chemistry and Biochemistry - R.W. Schurko 15