复旦大学无机化学IC13.pptVIP

3.3 The Noble Gases: Helium, Neon, Argon, Krypton, Xenon, and Radon 3.3.1 Introduction Once these elements were called as Group Zero, Inert gases and Rare gases. Since the lighter members are by no means rare and the heavier ones are not entirely inert, noble gases seems a more appropriate name and has come into general use during the past four decades. In the early 1960s, Neil Bartlett was studying the properties of platinum hexafluoride, PtF6. It is an extremely powerful oxidizing agent in comparison with F2. E0/V ΔH electron affinity/kJ mol-1 PtF6 2.87 700 F2 2.87 328 N. Bartlett accidentally exposed platinum hexafluoride to air, he noticed a change in color and he latter proved the composition of the new compound as O2+PtF6-. It is possible to remove one electron from the oxygen molecule and isolate the product: O2 + PtF6 → O2+PtF6- (paramagnetic, 2.46 BM) Bartlett realized that the first ionization energy of molecule oxygen is almost identical to that of xenon. O2 I1 = 12.2 eV; Xe I1 = 12.1 eV Furthermore, the dioxygenyl cation should be roughly the same size as a Xe+ ion because the radius of O2 is similar to that of xenon. Xe r = 210 pm (van der Waals radius); O2 r = 201 pm (rO + dO-O/2 = 140 + 121/2 = 201 pm) Hence, the lattice energies of the corresponding compounds should be similar. According to his calculation, the lattice energy of Xe+PtF6- was slightly bigger than that of O2+PtF6-. Ulattice (Xe+PtF6-) Ulattice (O2+PtF6-) ~10 kcal mol-1 He quickly proceeded to show that deep-red PtF6 vapor spontaneously oxidized Xe to produce an orange-yellow solid. Xe + PtF6 → Xe+PtF6- The first compound of inert gas was born. Since PM 6:45, March 23rd, 1962, Noble-gas chemistry had begun. 3.3.2 Compounds of Xenon 1. Xe – F2 system Within a few months, three fluorides of Xe had been synthesized. Thermal or photochemical activating the mixture