Chemistry 114: Fundamental Chemistry Third sample test, 2014. Name: ID: R = 8.31447 J/(mol. K) ln(K2/K1) = –(ΔH°/R)(1/T2 – 1/T1) ΔG = ΔG° + RT ln Q ΔG° = –RT ln K G = H –TS S = kBlnW Sm = S° – R ln p (for an ideal gas) Group** Period 1 1 5 6 7 8 9 10 11 12 13 17 18 4.003 5 6 7 8 9 10 Li Be B C N O F Ne 6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18 13 14 15 16 17 18 4 12 Na Mg Al Si P S 22.99 24.31 26.98 28.09 30.97 32.07 35.45 39.95 31 32 33 34 35 36 20 21 22 23 24 25 26 27 28 29 30 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As 38 39 40 41 42 43 44 45 46 47 48 49 Cl Ar Se Br Kr 72.59 74.92 78.96 79.90 83.80 50 51 52 53 54 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 85.47 87.62 88.91 91.22 92.91 95.94 127.6 126.9 131.3 85 86 55 56 72 73 74 (98) 75 101.1 102.9 106.4 107.9 112.4 114.8 76 77 78 79 80 81 118.7 121.8 82 83 84 Cs Ba * Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 132.9 137.3 87 7 16 1.008 37 6 15 2 39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.47 58.69 63.55 65.39 69.72 5 14 He 19 4 4 1 11 3 3 H 3 2 2 178.5 180.9 183.9 186.2 190.2 190.2 195.1 197.0 200.5 204.4 88 104 105 106 107 108 109 110 111 112 113 207.2 209.0 (210) (210) (222) 114 115 116 117 118 Fr Ra ** Rf Db Sg Bh Hs Mt Ds Rg Cn Uut Uuq Uup Uuh Uus Uuo (223) (226) Lanthanide Series* Actinide Series** (257) (260) (263) 57 58 59 60 (262) (265) (266) (271) (272) (277) 61 62 63 64 65 66 (?) (285) 67 68 (?) 69 (289) 70 71 La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 138.9 140.1 140.9 144.2 (147) 150.4 152.0 157.3 158.9 162.5 164.9 89 90 91 92 93 94 95 96 97 98 99 167.3 100 168.9 173.0 175.0 101 102 103 Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr (227) 232.0 (231) (238) (237) (242) (243) (247) (247) (249) (254) (253) (256) (254) (257) (?) (?) Short answer section (40 points). Underline the correct alternative. There is only one in each case. Answer all questions. (1) When we burn lithium in air, the major oxide formed is (a)Li2O (b)Li2O2 (c)LiO2 (d)Li2O3 (2) Which of these compounds is a Lewis acid (a) NH3 (b) BCl3 (b) CCl4 (d) SF6 (3) Aluminum oxide is (a) basic (b) acidic (c) amphoteric (d) none of the above. (3) At 0 K, the entropy of a pure crystalline substance becomes equal to /zero / the Gibbs free energy / the enthalpy/ infinity (4) Plotted against temperature, the entropy of a pure substance /always slopes upward / always slopes downward / usually but not always slopes upward / usually but not always slopes downward. (5) If you double the pressure of a mole of an ideal gas, keeping the temperature constant, the free energy relative to the standard free energy /doubles /decreases by a factor of 2/ increases by a factor RT ln 2 / decreases by a factor RT ln 2 (6) A solution of AlCl3 is expected to be /basic/neutral/acid/blue (7) When water boils at 1 bar pressure and approximately 100°C, which does not increase? /the entropy of the system/ the enthalpy of the system/ the Gibbs free energy of the system / the internal energy of the system. (8) In the solid state, lead monoxide PbO is (a) ionic (b) network covalent (c) molecular covalent (d) metallic. (9) For the reaction 2Na(s) + 2H2O (l) → 2 NaOH (aq) + H2 (g) at 1 bar, the entropy change is / positive /zero /negative/ I need a table of S° values to decide. (10) Which is not an expression of the second law of thermodynamics? /heat always flows spontaneously from hot to cold/ the entropy of the universe is always increasing/ one cannot extract work from a system by cooling it below the temperature of its surroundings/ the Gibbs free energy is always positive. (11) (extra credit) Which topic has Chancellor Harvey Perlman not addressed in his Perls of Knowledge video series (A clear sign the topic has jumped the shark) / the zombie apocalypse / ice cream from the Dairy Store / YOLO / Lady Gaga (thank heavens) Long answer section (60 points): complete 5 of 8 questions. Mark the ones you want graded. If you do not, we will grade the first three you in any way attempt. 1) Bromine data at 25°C. ΔHf° kJ/mol ΔGf° kJ/mol S° J/(mol.K) Br2 (g.) 30.91 3.11 245.5 Br2 (l.) 0 0 152.2 Predict the vapor pressure of bromine liquid at 25°C and the boiling point at 1 bar pressure. RT ln K = RT ln pv = –3110 J mol so p = 0.285 bar. At the boiling point ΔG = 0, and ( G/ T)p = –S, so ΔT ~ –ΔG/ΔS = 3110/(245.5 – 152.2) = 33.3, so Tb = 33.3 + 25 = 58.5°C. 2) Chlorate ions (ClO3–) disproportionate in strong acid solution to give chlorine dioxide (ClO2) and perchlorate (ClO4–). Write a balanced chemical equation for the reaction. 3 ClO3– + 2 H+ → 2 ClO2 + ClO4– + H2O 3) (The rich get heavy metal poisoning too!) You are feeding your baby with orange juice via a silver spoon (you know how that is!) The orange juice is at pH 3. Assuming each spoonful of the orange juice comes to equilibrium with the spoon and with atmospheric oxygen at 0.2 bar, what will the concentration of silver ions be in the orange juice? (hint; write down a balanced equation for the oxidation of silver by oxygen under acid conditions first) Ag+ + e− ⇌ Ag(s) : E° = +0.7996 V O2(g) + 4 H+ + 4 e− ⇌ 2 H2O : E° = +1.229 4Ag(s) ⇌ 4Ag+ + 4e− : E° = –0.7996 V O2(g) + 4 H+ + 4Ag(s) ⇌ 2H2O + 4Ag+: E° = 0.4294 V Q = [Ag+]4/(pO2[H+]4) = [Ag+]4/2.0 × 10-13 At equilibrium (RT/NF)ln Q = E° = 0.4294 V, so ln Q = 66.9, so Q = 1.08 × 1029 so [Ag+]4 = 2.16 × 1016, so [Ag+] =1.2 × 104. The spoon will dissolve completely! (given enough time) 4) Maltose binds to maltose binding protein with the following equilibrium Maltose + MBP ⇌ Maltose-MBP. It has an equilibrium constant of 180,000 at 300 K, changing to 44,000 at 277 K. Determine ΔH° and ΔS° for the reaction, and ΔG° at 300 K. ΔG° = –RT ln K = –3.0 × 104 J/mol ΔH° = –R(ln 180000/44000)/(1/300-1/277) = 4.2 × 104 J/mol ΔS° = (ΔH° – ΔG°)/T = 241.7 J mol–1 K–1 5) In the synthesis of gaseous methanol from CO and H2 according to the reaction CO(g) + 2 H2(g) ⇌ 2 CH3OH at 483 K, the equilibrium pressures measured were pCO = 0.911 bar; pH2 = .822 bar; pCH3OH = 0.0892 bar. Calculate the equilibrium constant Kp and the standard Gibbs free energy change for the reaction. K = 0.08922/(.911 × .8222) = .0129 ΔG° = –RT ln K = 17.4 kJ/mol 6) What will be the peak voltage of a battery composed of solid lithium and solid MnO2 plates, and an electrolyte containing an aqueous solution of 0.01 M H+, 1 M Li+ and 0.1 M Mn2+? If one plate is composed of 100 g of pure MnO2, what should the mass of Li on the other plate be, and how much total energy in J will the battery provide? Li+ (aq) + e– → Li (s) E° = –3.040 V MnO2 (s) + 4 H+ (aq) + 2 e– → Mn2+ (aq) + 2 H2O (l) E° = 1.23V + 2+ MnO2 (s) + 4 H (aq) + 2 Li (s) → Mn (aq) + 2 H2O (l) + 2 Li+ (aq) E° = 4.27V E = E° – (RT/NF) ln Q = 4.06 V 100 g = 100/(54.94+2× 16)mol = 1.15 mol, reacts with 2.30 mol Li = 16.0 g gives 2.30 mol electrons = 2.22 × 105 C × 4.06 V = 9.02 × 105 J 7) Tl3I4 is the empirical formula of a compound of unknown structure. Write formulas of it in terms of the oxidation state of thallium [e.g. Fe3O4 is actually Fe(II) Fe(III)2O4 ] The total oxidation number of I is –4; there is no way 3 Tl atoms can have an oxidation number of +4. So let’s try doubling it to Tl6I8; now we can make it Tl(I)5Tl(III)1I8
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