Session #9: Homework Solutions

Session #9: Homework Solutions Problem #1 Estimate the ionic radius of Cs+. The lattice energy of CsCl is 633 kJ/mol. For CsCl the Madelung constant, M, is 1.763, and the Born exponent, n, is 10.7. The ionic radius of Cl– is known to be 1.81 Å. Solution Mq1q2 ⎛ 1⎞ 1 − ⎟ and ro = r + + r − ⎜ Cs Cl 4πε oro ⎝ n⎠ Elattice = Solve first for ro Mq1q2NAν 4πεoElattice ro = 1⎞ 1.763(1.6 x 10-19 )2 6.02 x 1023 ⎛ 1 − = ⎜ n ⎟⎠ ⎝ 4π8.85 x 10-126.33x105 = 3.50 x 10-10m = 3.50 Å = r Cs+ ∴ r Cs+ 1 ⎞ ⎛ ⎜1 − 10.7 ⎟ ⎠ ⎝ + r Cl- = 3.50-1.81 = 1.69 Å Problem #2 (a) CFCs have been implicated in ozone depletion. Show that when Freon 12 (CCl2F2) is exposed to ultraviolet radiation, the compound decomposes to produce chlorine. (b) Draw the Lewis structure of Freon 12 and indicate the polarities of each bond within this compound. (c) Determine the percent ionic character of the C--Cl and C--F bonds. DATA: Average Bond Energies (kJ/mol) Single Bonds Multiple Bonds H-H F-F Cl-Cl C-C C=C C ≡C 435 155 242 347 610 836 Solution (a) Chlorine will be liberated if the C-Cl bond breaks, therefore, compute its strength and show that ultraviolet photons have enough energy to break the bond. EC − C x ECl − Cl + 96.3(χ C − χ Cl )2 EC − Cl = 347 x 242 + 96.3(2.55 - 3.16)2 = = 326 x 103/6.02 x 1023 = 5.41 x 10-19 J/bond photon will break ∴ this bond if Eph > Ebond ⇒ critical λ is λ = hc Ebond = 6.6 x 10-34 x 3 x 108 -19 5.41 x 10 = 3.66 x 10-7 m which lies in the u.v. part of the electromagnetic spectrum. (b) Draw the Lewis structure of Freon 12 and indicate the polarities of each bond within this compound. or (c) C-Cl C-F or Δχ = 0.61 → ~9% ionic character Δχ = 1.43 → ~40% ionic character Problem #3 The compound trichloroethylene has the composition C2Cl3H. (a) Formulate this compound in “Lewis” notation. Example: H CH4 = H C H H (b) List the types of atomic orbitals which, upon overlap, lead to the formation of the bonds indicated in (a). (c) List all bonds (number and type) involved in the formation of this compound. Solution (a) C2Cl3H in Lewis notation: Cl H C=C Cl Cl Note that the H may be located on any one of the 4 (sp2) hybrid orbitals without changing the properties of the compound. (b) sp2 sp2 sp2 On each carbon there are: three equivalent sp2 bonding orbitals in a plane and one p orbital normal to the sp2 plane. p On each chlorine there is: one singly occupied p orbital. Cl H On the hydrogen we have: one singly occupied 1s orbital. (c) 2 sp2 − sp2 orbitals → 1σ Cσ -C 2 p–p orbitals → 1π C π − C 6 bonds 3 sp2 − p orbitals → 3σ C-Cl 1 sp2 − s orbitals → 1σ C-H Problem #4 Frequently the statement is made that the crystal energy ( Δ Ecryst) is predominantly given by the attractive energy term. How can you account for this approximation? Solution Ecryst = K (1 – 1/n) = K – 1/n K where –1/n K is the repulsive contribution to Ecryst ⋅ 1/n ≅ 1/8. This means only ~12% of the total crystal energy. Problem #5 For benzene (C6H6), which has a schematic carbon arrangement: C C C C C C (a) Determine the total number and types of covalent bonds. (b) For each bonding type, determine the bonding orbitals which, by overlap, lead to their formation. Solution C (a) C C C C From the schematic we recognize three single and three double carbon–to–carbon bonds which are respectively of the σ (sigma) and σ + π (sigma + pi) variety. Left out in the schematic are the six C–H bonds which are of the σ variety: H C C H In C6H6, C we have 12 σ and 3 π bonds. H H C C C = C6H6 H C H (b) In the ring structure of benzene we have three double bonds, which means that all six carbon atoms are sp2 hybridized. Accordingly: 3 π bonds involve lateral (p–p) obrital overlap. 6 (C–C) σ bonds involve (sp2–sp2) orbital overlap. 6 (C–H) σ bonds involve (sp2–s) orbital overlap. (It should be noted that the experimentally determined bond energy for the carbon ring is larger than the sum of the bond energies of the double plus single bonds. This increased bond energy is attributed to the existence of alternating double bonds which permit the establishment of “equivalent resonance structures” in which the double bonds are said to be delocalized: Problem #6 Why is double bonding encountered in some carbon compounds, but not in germanium compounds – although both exhibit sp3 hybridization? Solution Double bond formation, the result of lateral p orbital overlap, is contingent on close approach of the atoms. Such approach is possible for carbon with its K shell, but not for the larger germanium with its fully occupied M shell. Problem #7 List the individual steps with the corresponding chemical equations used in constructing a Born-Haber cycle for the formation of CaBr2 from the element and identify those which you expect to be exothermic. Solution ΔHvap (+) 1) Ca(s) → Ca(v) 2) 3) Br2 (g) → 2Br • ++ Ca → Ca ΔHdissoc (+) + 2e − + 3a) Ca → Ca + 1e- ΔHioniz (+) 3b) Ca+ → Ca++ + 1e− ΔHioniz (+) 4) - 1− Br + 1e → Br 2+ 5) Ca 1− + 2Br → CaBr2 EA (-) → exothermic DEcryst (−) → exothermic ___________________________________________________________________ Δ Hreaction = Δ Hvap + Δ Hdissoc + 1 Δ Hioniz + 2 Δ Hioniz + 2EA + Δ Ecryst (it is acceptable to note Ca → Ca++ + 2e– if you realize that 1 and 2 ionization is involved) Problem #8 (a) Given the ionic radii, Cs+ = 1.67Å, Cl– = 1.81Å, and the Madelung constant M(CsCl) = 1.763, determine to the best of your ability the molar Crystal energy ( Δ Ecryst) for CsCl. (b) Not given additional data, do you expect the value obtained to be larger or smaller than theoretical, and by how many percent do you anticipate to be off? Solution (a) Given the radii Cs+ = 1.67Å and Cl– = 1.81Å, we can assume that ro is the sum of the two. However, we need to know the exponential constant of the repulsive term which is not provided. Considering only the attractive force: ΔEcryst = - e2NAMQ1Q2 4πε oro where: Q1 = Q2=1 M=1.763 NA = 6.02 x 1023 particle/mole ΔEcryst = - (1.6 x 10-19coul)2 x 6.02 x 1023 x 1.763 x 1x 1 4π 8.85 x 10-12 x(1.81 + 1.67)x10−10 m = 7.02 x 10 5 J/mole (b) Because we didn’t include the repulsive part, we expect the theoretical energy to be smaller by 1/n times then calculated above. Because n is in the range of 10 we are off by around +10%