Model answers for CH103 (Sept. 14, 2011) 1.

The experimentally observed first ionization potentials (in KJ mol-1) of boron and carbon are 801 and 1086 respectively. Their second ionization potentials are 2426 and 2352 respectively. (0.5+0.5) (a) Explain why the first ionization potential is higher for carbon than that of boron? C 1s2 2s2 2p2 B 1s2 2s2 2p1 Since the Zeff is more in case of C as compared to B for the 2p electron, the ionization potential is high for C as compared to B. (1/2 mark) P.S.: By showing the stable gas configuration for B after removing an electron cannot fetch mark. (b) Explain why the second ionization potential is higher for boron than that of carbon? + C+ 1s2 2s2 2p1 B 1s2 2s2 Removal of an unpaired electron from carbon (C+) is easier as compared to the paired 2s electron from boron (B+). Hence, the second ionization potential of C is less than B. 2. If an element with atomic number 115 is ever discovered, answer the following. [Z for Rn is 86] (0.5 + 0.5) (a) What will be its IUPAC name and the symbol? Ununpentium, Uup (both name and symbols should be correct -- mark) P.S.: Both the name and symbol should be correct to fetch mark. If the first letter in the symbol is not the capital letter, you loose mark. (b) List the other elements present in the same group to which this element belongs. N, P, As, Sb & Bi (any four correct --- pl. give mark)

3. When a cation is surrounded by 4, 6, 8 or 10 of the same anions, what happens to the size of the central cation and why? (1.0) The size of the central cation increases as the number of surrounded anions increase. (1/2 mark) As the number of surrounded anions increase, the volume or the size of the coordination sphere increases owing to the inner anion-anion repulsions. (1/2 mark) P.S.: Answers such as polarization effect is not acceptable. Answer such as the number of ligands are more, the attraction is more and hence the size is large --This is a wrong answer. 4. Arrange the four elements, Li, N, Si & Cl, in the order of their increasing atomic size. (1.0) Ans: N < Cl < Si 1 < Li (1 mark)

{P.S.: If first and last are correct --- mark} 5. Almost all the elements in the lanthanide series, eg., from La to Lu, exhibit similar atomic volumes, while the deviations were observed mainly with Eu (Z=63) and Yb (Z=70). Answer the following. (a) Explain the fact that the atomic volumes in this period are almost constant. As the added electrons go into the inner or (n-2)f or 4f orbitals mainly, the available electrons for the interaction (metallic bond) are 5d1 6s2, hence almost similar atomic volume per mole. P.S.: Just by writing lanthanide contraction, though correct for the size alone of a single atom, will not fetch any mark. Even the answer such as that the atomic radius is same cannot fetch mark, because that will not imply anything regarding the inter-atmoic interactions as well as volume, hence no marking for this. Even the answer such as the incoming electron going into the interior f-orbital and Zeff increases will NOT BE CONSIDERED as complete answer for this. (b) Give reasons for the deviation of the volume in case of Eu and Yb from the rest of the period. In these elements, due to f7 and f14 configurations, the valence shells have only two electrons for the interaction (metallic bond formation) and hence the volume changes (increases). P.S.: Just by writing that the half-filled and fully-filled f-orbital are stable is not an interpretation and hence will not fetch any mark. 6. An element with Z = 74 is given. (a) Write the electronic configuration of this element in the order of increasing orbital energies starting from Xe (Z = 54). (0.5) (1/2 mark) [Xe] 4f14 5d4 6s2 OR 4f14 5d5 6s1 P.S.: Since the question asks for an increasing orbital energies, no other order will fetch mark. (b) Compute Zeff for a 5d electron in this atom. (0.5) 74 [11x0.35] 60x1 = 74 3.85 60 = 10.15 OR 74 [12x0.35] 68 x 1 = 74 4.2 -60 = 9.8