HW 2. CHEM 481 Chapters 3 & 5 Chapter 3. Energetics of Ionic Bonding
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1 HW 2. CHEM 481 Chapters 3 & 5 Chapter 3. Energetics of Ionic Bonding Name: 1. Give coordination number for both anion and cation of the following ionic lattices. a) CsCl Structure: b) Rock Salt Structure: c) Fluorite Structure: d) Sphalrite Structure: e) Wurtzite: f) Rutile: 2. Calculate the number of formula units in the unit cell of the following metallic and ionic compounds. a) NaCl(fcc) b) CsCl(bcc) c) ZnS(fcc) d) CaF 2 (bcc) 3. What is Coulombs law how it applies to ionic bond? 4. What is lattice energy? Take NaCl as an example. 5. Place the following compounds in order of increasing lattice energy: a) magnesium oxide b) lithium fluoride c) sodium chloride. Give the reasoning for this order.
2 6. Explain the lattice energy and melting point trends: Compound Cation radius (Angstroms) Anion radius (Angstroms) Melting Point (Centigrade) Lattice Energy (kcal/mol) MgCl CaCl MgO CaO Why is Madalung constant for NaCl is significantly different from CaF 2 value and why is it different for different ionic lattice types? Ionic Solid Madelung Constant Coor. # Lattice Type A : C NaCl : 6 Rock salt CaF : 4 Fluorite 8. Calculate the first two terms of the series for the Madelung constant for the cesium chloride lattice. How does this compare with the limiting value? 9. In calculating lattice energy, why should Coulombs law equation is multiplied by the Avogadro s number, N and Madelung constant, A? N z 2 e 2 N A z 2 e 2 Lattice Energy = x N x A = o r 4 o r
3 10. In the correction to lattice energy what is factor n in Born-Lande equation accounted for and how it relate to electronic configuration? 11. Using the Born-Lande equation, calculate the lattice energy of cesium chloride. N A z 2 e 2 1 Lattice Energy = ( ) 4 o r n 12. What are Born-Mayer and Kapustinskii equations? How are they different from the Born-Lande equation? 13. What is a Born-Haber cycle? 14. Calculate the Lattice energy of NaCl from following thermodynamic data: Steps Ho, kj 1. Vaporization of sodium: Na(s) Na(g) Decomposition of Cl 2 : 1/2 Cl 2 (g) Cl(g) Ionization of sodium: Na(g) Na + (g) Electron affinity to chlorine: Cl(g) + e - Cl - (g) -349
4 5. Formation of NaCl(s): Na(g)+1/2Cl 2 (g) NaCl(s) Construct a Born-Haber cycle for the formation of aluminum fluoride. Do not perform any calculation. 16. Define following terms: a) Enthalpy of solution, H solution : b) Enthalpy of hydration, H hydration : c) Solvent-solvent intermolecular attractions, H solvent-solvent : 17. How is Enthalpy of solution, H solution, Enthalpy of hydration, and Lattice energy are related? 18. Predict the solubility of following ionic compounds: Lattice Energy(U) H hyd, M + H hyd, M - LiF LiI CsI MgF a) LiF: b) LiI:
5 c) CsI: d) MgF 2 : 19. Give rational explanation to the solubility rules in terms of ioin sizes, lattice energy(u), H hyd, and H solution. a) All compounds containing alkali metal cations and the ammonium ion are soluble. b) All compounds containing NO 3 -, ClO 4 -, ClO 3 -, and C 2 H 3 O 2 - anions are soluble. 20. Calculate the enthalpy of formation of calcium oxide using a Born-Haber cycle. Obtain all necessary information from the data tables in the Appendices. Compare the value that you obtain with the actual entropy measured value of H f (CaO(s)). 21. Although the hydration energy of the calcium ion, Ca 2+, is much greater than that of the potassium ion, K +, the molar solubility of calcium chloride is much less than that of potassium chloride. Suggest an explanation.
6 HW 2. CHEM 481 Chapters 3 & 5 Chapter 5 Redox Chemistry Name: 1. Which of the following reactions is redox? a) NaCl + AgNO 3 AgCl + NaNO 3 b) NaOH + HCl NaCl + H 2 O c) Zn + 2HCl ZnCl 2 + H 2 d) 2Cr + 6HCl 2CrCl 3 + 3H 2 e) MnO 2 + 4HBr Br 2 + MnBr 2 + 2H 2 O 2. Separate the reduction and oxidation half reactions in following chemical equations. a) Zn + 2HCl ZnCl 2 + H 2 b) MnO 2 + 4HBr Br 2 + MnBr 2 + 2H 2 O c) 10K + 2KNO 3 N 2 + 6K 2 O 3. Balance following reactions that take place and give the sum of stoichiometric coefficients. a) Cr 2 O 7 2- (aq) + Cl - (aq) Cr 3+ (aq) + Cl 2 (g) (acid solution) b) Br - (aq) + MnO 4 (aq) Br 2 (g) + Mn 2+ (aq) (acid solution) c) Al(s) + MnO 4 - (aq) MnO 2 (s) + Al(OH) 4 - (aq) (basic solution) 4. Construct a Galvanic cell employing following reactions: a) Ni(s) + Cu 2+ (aq) Ni 2+ (aq) + Cu(s) b) Zn(s) + 2H + (aq) Zn 2+ (aq) + H 2 (g)
7 5. Using the E 0 values given in the table calculate the E o cell for reactions in problem 4 and identify following: a) two half reactions; b) anode; c) cathode; d) direction of electron flow through the external wire. 6. Calculate the G 0 value for reactions in problem Using Ellingham diagram find out the minimum temperature required for the reduction of SiO 2 by C. Please write the redox reactions involved. 8. Estimate the potential difference required to reduce TiO 2 to metal at C. 9. Using Lattimer diagram(appendix 2) calculate the E 0 for the reduction of HClO 3 to HClO in aqueous acidic solution. 10. Write balanced half-reactions for the reduction of NO to N 2 O and N 2 O to N 2 in basic solution.
8 Is N 2 O thermodynamically stable with respect to disproportionation to NO and N 2 in basic solution? What is G o?
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