課程名稱︰無機化學二 課程性質︰必修 課程教師︰林英智 開課學院：理學院 開課系所︰化學系 考試日期（年月日）︰101/4/11 考試時限（分鐘）：130 是否需發放獎勵金：是 （如未明確表示，則不予發放） 試題 : Part I. Single Choise(30%: 2% each) 1. Which of the dfollowing orders is correct? (A)Basicity toward proton: pyridine>2-t-butylpyridine>2-methylpyridine> 2,6-dimethylpyridine (B)Basicity toward BMe3: quinuclidine<triethelamine (C)Acidity: H3O+>Si(OH)4>NH3>CH3GeH3 (D)Basicity of oxides: BaO>Al2O3>B2O3 2. According to hard-soft acid base theory, how many of following reactions will go right?(i.e. Keq>1) (a)CuI2+2CuF←→CuF2+2CuI (b)CoF2+HgBr2←→CoBr2+HgF2 (c)AlI3+3NaF←→AlF3+3NaI (d)TiF4+2TiI2←→TiI4+2TiF2 (e)R3P-BBr3+R3N-BF3←→R3P-BF3+R3N-BBr3 (f)SO2+Ph3P:HOCMe3←→Ph3P-SO2+HOCMe3 (g)H3B-CO+BBr3←→H3B+Br3B-CO (h)HF+NaI←→HI+NaF (i)CH3HgI+HCl←→CH3HgCl+HI (j)Ag(NH3)++F-←→AgF+NH3 (k)NH3+CaF+←→Ca(NH3)2++F- Unless otherwise stated, assume gas-phase or hydrocarbon solution and 298K (A)3 (B)5 (C)7 (D)8 (E)9 3. About reaction of Lewis acids and bases, which one of the following pairs is NOT correct? (A)(Me)3Si-I_AgBr→(Me)3Si-Br+AgI Metathesis reaction (B)SO3+CH3OCH3→O3S-O(CH3)2 Complex formation (C)AsF3+SbF5→[AsF2]+[SbF6]- Complex formation (D)(CH3)2O-BF3+pyridine→CH3OCH3+F3B-pyridine Displacement reaction 4. The pKa values of HClO4, HSO4-, H3AsO4, HMnO4 are x,y,z,t, respectively. According to Pauling's rule, which of the following srts is correct? (A)(x,y,z,t)=(-7,2,5,-1) (B)(x,y,z,t)=(-7,3,3,-7) (C)(x,y,z,t)=(-1,5,2,-7) (D)(x,y,z,t)=(-8,1,3,-7) 5. Which of the following statements is NOT correct? Use the resox potential information of the digure shown below.(Plutonium in acidic solution) +1.03 Z ┌────────────┐ ┌──────────────┐ ∣ ↓ │ ↓ 2+ X + +1.04 4+ +1.01 3+ -3.5 2+ -1.2 PuO ———→PuO ————→Pu ————→Pu ————→(Pu) ————→Pu 2 2 │ ↑ └─────────────────────┘ Y (A)(X,Y,Z)=(+1.02, -1.25, -2.00) (B)PuO2+ tend to disproportionate to Pu4+ and PuO22+ (C)Pu4+ is stable in conectrated acid (D)Pu3+ tend to disproportionate to Pu4+ and (Pu)2+ 6. For the oxidation-redction reaction below(not balanced) 2- 2+ 3+ 2- S O + Cr → Cr + S O 4 6 2 3 The appropriate half-reactions are: 2- - 2- 0 S O +2e → 2S O E =0.17V 4 6 2 3 3+ - 2+ 0 Cr + e → Cr E =-0.50V 0 Calculate E and K (A)E=1.17, K=10^39.6 (B)E=0.67, K=10^52.1 (C)E=0.76, K=10^22.6 (D)E=1.17, K=10^91.1 7. Which of the following statements is NOT correct? (A)The acidity of a series of colso-boron hydirdes is in the order of: B16H20<B14H10<B6H10<B5H9 (B)Inindustry, Cl2 can be obtained by electrolyzing NaCl/H2O solution (2Cl- →Cl2+2e- E=-1.36V; H2O→1/2O2 E=-1.23V) (C)In3+ is stable than In+, however Tl3+ is less stable than Tl+ due to the inert pair effect (D)Copper could be extracted from its ores by aerial oxidation 8. In the following transitions (toward right) in aqueous solution, which one is correct? (A)CN-+MnO →CVO-+MNO2 in basic solution (B)Br2 →BrO3-+Br- in acidic solution (C)(S2O3)2-+I2 →(S4O6)2-+2I- same potential in acidic or basic solution (D)ClO3-+Cl- →Cl2+ClO2- in basic solution 9. Given the following cluster compounds, which one of the pairs is correct? (A)[C2B9H11]2-, closo (B)As2C2B7H9, nido (C)SiC2B4H10, hypo (D)C8H8, arachno 10.Which of the following descriptions about borazine and its derivatives is NOT correct? (A)Borazine hase higher reactivity than benzene (B)Lewis acid site is B and Lewis base site is N (C)B10H14+C2H2 →1,2-C2B10H12, which is the most thermadynamically stable isomer (D)If the boron cluster B5H11 has three different boron reasonance in proton- decoupled 11B-NMR, it ha styx number=(3203) 11.Which of the following nomenclature is correct? (A)[Co(N3)(NH3)5]SO4, monoazidopentaamminecobalt(III) sulfate (B)[Co(en)2CO3]Br, carbonobis(ethylenediamine)cobalt(III) bromide (C)[Ag(NH3)2][BF4], diamminesilver(I) tetrafluoroborate (D)Fe(S2CNMe2)3, tris(dimethyldithiocarbamate)iron(III) 12.What is the emf of the following concentration cell? (assuming ideal behavior) 2+ 2+ 2+ - Mg|Mg (0.24M)||Mg (0.53M)|Mg; (Mg +2e →Mg, E=-2.37V) (A)-2.38V (B)+0.010V (C)-2.36V (D)-0.010V 13.Choose the INCORRECT statement (A)The total number of isomers for [Co(NH3)2(H2O)2Cl2]+ including enantiomers are 6 (B)Octahedral complex M(AB)2CD where (AB) is a bidentate ligand, has 10 isomers (C)[Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4 are ionization isomers (D)[Pd(κN-NCS)2(AsPh3)2] and [Pd(κS-SCN)2(AsPh3)2] are linkage isomers 14.Which of the following six ligands in order of increasing ability to form stable complexes is correct? (1) (2) ／￣＼ (3) ／￣＼ (4) NH HN NH HN ／￣＼ H NNH ／ ＼ ／ ＼ H N NH 2 2 ∣ ∣ ∣ ∣ 2 2 ＼ ／ ＼ ／ NH H N NH HN 2 2 ＼ˍ／ (5) (6) ／＼ ／＼ ∣ ∣ ∣ ∣ ＿NH NH NH NH ╱ 2 2 2 ╲＿ NH NH ∣ ∣ 2 ＼／ (A)1>4>6>5>2>3 (B)3>2>5>4>6>1 (C)3>5>2>6>4>1 (D)5>2>3>6>4>1 15.Which of the following order or statement is correct? (A)Oxidation ability: H2Cr2O7<MoO3<WO3 (B)Stability: Re7+>Tc7+>Mn7+ (C)The element with the group oxidation state is the most stable species (D)[V(O)2(ox)2]3- has trans-dioxometal structure and both [Re(O)2(py)4]+ and [Mo(O)2(CN)4]4- have cis-oxometal structure Part II. Questions (70%: 10% each) 1. (i)Use Drago's E and C parameters t calculate ΔH for the reaction of pyridine and BF3 and of pyridine and B(Me)3. Compare your results and the reported experimental values of -71.1 and -64 KJ/mol for pyridine-B(Me)3 and -105 KJ/mol for pyridine-BF3 (ii)Explain the dofferences found in part (i). In terms of the structure of BF3 and B(Me)3 (iii)Explain the differences in terms of HSAB theory. (hint: Drago-Wayland equation -ΔH-EaEb+CaCb) (kcal/mol) Acid Ca Ea B(Me)3 1.70 6.14 BF3 1.62 9.88 Base Cb Eb pyridine 6.40 1.17 2.Choose the proper item and explain: (i)Strongest base toward proton: α,β-lactam; α,γ-lactam, α,δ-lactam and α,ε-lactam (ii)Strongest base toward B(Me)3: pyridine, 2-t-butylpyridine, 2-methylpyridine, 2,6-dimethylpyridine (iii)Strongest Lewis acid: BeCl2, BCl3 3.Given that -0.125 +1.510 O ————→HO ————→H O 2 2 2 2 0 Construct the Frost diagram and calculate the value of E for the reaction 2HO2→O2+H2O2 Comment on the thermadynamic tendency of HO2 under disproportionation. 4.The cjloro groups in [Re2Cl8]2- are eclipsed, but the chloro groups in [OsCl8]2- are staggered. Offer an explanation. 5.Draw the all isomers of M(AB)2D2 (including enantiomers) and classify their absolute configuration, where (AB) is a bidentate lugand. 6.Construct the Pourbaix diagram for H2). Given that 2H2O → O2 + 4H+ + 4e- E=-1.23V and the standard reduction potential of hydrogen. 7.The stepwise formation constants for complexes of NH3 with [Cu(H2O)6]2+ are log Kf1=4.15, log Kf2=3.50, log Kf3=2.89, log Kf4=2.13, and log Kf5=-0.52. Suggest a reacon why Kf5 is so different. --

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