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Homework Assignment 8 Chemistry 118 - Principles of Chemistry Spring, 2018 Problem Assignment 8 (due Friday, April 13, 2018) 1. Calculate DG° for each of the following reactions: Fe2O3(s) + 3/2 C(s) ® 2 Fe(s) + 3/2 CO2(g) Fe2O3(s) + 3 C(s) ® 2 Fe(s) + 3 CO(g) Fe2O3(s) + 3 CO(g) ® 2 Fe(s) + 3 CO2(g) From your results, determine whether C or CO is the better reducing agent for the conversion of Fe2O3 to Fe metal. Explain. 2. The reaction of NO and Cl2 leading to the formation of NOCl is presumed to proceed in the gas-phase by the two-step mechanism shown below: k1 NO + Cl2 Û NOCl2 k-1 k2 NO + NOCl2 ® 2 NOCl a. If the second-step is assumed to be the rate-determining step, then derive a rate law expression for the production of NOCl for this proposed mechanism. b. Alternatively, now using the steady-state approximation, derive the corresponding rate law for the production of NOCl for this proposed mechanism. 3. Silver Iodide, which is used in the preparation of photographic emulsions and for cloud seeding, adopts the zinc blende structure with a cell edge length of 6.473 Å. Calculate the density of AgI and the shortest distance between the Ag+ cation and the I- anion in this lattice. 4. Calculate the equilibrium constant under standard conditions for the production of hypochorite ion from the reaction of dichlorine oxide with hydroxide. - - Cl2O(g) + 2 OH (aq) ® 2 OCl (aq) + H2O(l) 5. Draw the Lewis structures and predict the molecular shapes for the following fluorine containing compounds: + - - OF2, BrF3, ClF2 , AsF6 , BF4 6. Thermal cracking is employed by the petrochemical industry to reduce large hydrocarbon molecules into smaller more useful organic compounds. Upon thermal cracking at 500 °C, n-butane (C4H10) decomposes to ethane (C2H6) and ethylene (C2H4). CH3CH2CH2CH3(g) ® CH3CH3(g) + CH2=CH2(g) CH3CH2CH2CH3(g) CH3CH3(g) CH2=CH2(g) DHf° (kJ/mol) -124.73 -84.68 52.26 DS° (J/K mol) 310.03 229.49 219.45 a. Calculate the equilibrium constant for this reaction at 25 °C. b. Calculate the equilibrium constant for this reaction at 500 °C. 7. Under acidic conditions, chlorous acid, HClO2, disproportionates to chlorate, - ClO3 , and hypochlorous acid, HClO. 1.21 v 1.65 v - ClO3 ® HClO2 ® HClO a. Write the balanced equation for the disproportionation of chlorous acid. b. Determine the standard cell potential and the equilibrium constant for this disproportionation reaction at 25.0 °C. - c. Determine the reduction potential for the reduction of ClO3 to HClO under acidic conditions. Write a balanced equation for this reduction half reaction. 4- 8. The reduction of perxenate ion, XeO6 , to xenon is so favored 2+ - thermodynamically in acidic solution that it will oxidize Mn to MnO4 , which is one of the strongest common oxidizing agents found in a chemistry lab, with the evolution of elemental oxygen. Write a balanced equation for this redox reaction. 9. A commercial fluorine cell generates 3.3 kg of fluorine gas per hour by the electrolysis of KF•2HF. Calculate the average current passing through this cell. 10. Recently, the annual total consumption of carbonated beverages in the United States reached 63 billion 12-ounce cans or bottles. If a 12-ounce can has a volume of 355 mL and the concentration of dissolved CO2 is 0.15 M, then calculate the total mass of CO2 used to make carbonated beverages during that year. 11. Dioxygen difluoride, O2F2, is a potent fluorinating agent. It is made by the irradiation of a mixture of O2 and F2 at -196 °C. Draw the Lewis structure for this molecule and determine the bond order of each bond. 12. When chlorine gas is bubbled through a basic solution containing iodide ions, chloride ions and iodate ions are produced. If 0.216 L of chlorine gas at 0 °C and 0.985 atm is needed to react completely with 50.0-mL of a iodide solution, then determine the initial concentration of the iodide in that solution. 2- 13. Under acidic conditions, sulfurous acid, H2SO3, disproportionates into SO4 and S. a. Write a balanced equation for this disproportionation reaction. b. The reduction potential diagram is given below for [H+] = 1.0 M. Calculate the cell potential for this disproportionation reaction. 0.172 v 0.450 v 0.140 v 2- 2- SO4 ® H2SO3 ® S ® S c. Calculate DG° and the equilibrium constant for this reaction at 25 °C. 14. Consider the lead-silver battery (Pb | Pb2+ (0.100 M) || Ag+ (0.250 M) | Ag). 2+ + E°red (Pb /Pb) = -0.126 volts, E°red (Ag /Ag) = 0.800 volts a. Calculate the cell potential when this battery is first connected at 25 °C. b. Sodium sulfate was added to the compartment containing the lead half- 2- cell until [SO4 ] = 0.100 M. If the measure cell potential is 1.096 volts, determine the concentration of [Pb2+] ion remaining in solution and the value of Ksp for PbSO4. 15. Ethanol, C2H5OH, is produced commercially by the fermentation of the starch in grains. The molar heat of combustion of ethanol is -1368 kJ/mol. a. Calculate the number of grams of ethanol that must be burned to raise the temperature of one-liter of water from 20.0 to 90.0 °C. b. If the molar heat of formation of CO2(g) and H2O(l) are -393.5 and -285.8 kJ/mol, respectively, then calculate the molar heat of formation of C2H5OH. .
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