UNIVERSITY OF LONDON
BSc/MSci DEGREE – June 2000, for Internal Students of the
Imperial College of Science, Technology and Medicine
This paper is also taken for the relevant examination for the
Associateship
INORGANIC CHEMISTRY I
Monday 19th June 2000, 9.30 – 12.30
ATTEMPT ALL QUESTIONS
USE A SEPARATE ANSWER BOOK FOR EACH
QUESTION
INORGAN1J2000 Turn over
Q1 Concepts of Inorganic Chemistry
Answer part (a) AND two of the parts (b), (c) AND (d)
(a) Show how the quantum number rules and the Pauli exclusion principle provide a
basis for the structure of the modern periodic table comprising 18 groups.
(15 marks)
(b) Describe the relationship between the energy of a photon incident upon a metallic
surface and the kinetic energy of the photoelectron released from the surface.
(5 marks)
(c) Describe the envelope of electron probability in a 2pz atomic orbital by means of a
properly labelled diagram.
(5 marks)
(d) Explain why the carbon atom possesses two unpaired electrons having identical
spin quantum number values.
(5 marks)
INORGAN1J2000 Page 1
Q2 Inorganic Reactivity
Answer parts (a) and (b) and EITHER part (c) OR part (d).
(a) Define the term Lewis acid. Give an example of a Lewis acid–base adduct.
Identify the following as hard or soft acids or bases: Li+, CN-, Cl-, Ag+.
(4 marks)
(b) Complete and balance the following equation. Identify which species is
oxidised and which is reduced. (4 marks)
[BH4]- + H2O → H3BO3 + H2
Above pH 9, sodium tetrahydroborate can be crystallised from aqueous
solution. Explain this. (2 marks)
(c) Show the important energetic differences between the acid dissociation
reaction in water,
HA(aq) + H2O H3O+ (aq)+ A- (aq)
and in the gas phase:
HA(g) A- (g)+ H+(g)
Give an example of a series of acids or bases that differ in their gas phase and
solution properties. (15 marks)
(d) Aluminium metal is prepared on an industrial scale electrochemically from
alumina (Al2O3) in Hall-Heroult cells with carbon anodes. Give a balanced
equation to describe this reaction. (3 marks)
Under the conditions used, the Gibbs free energy of this reaction
is +750 kJ mol-1
What is the minimum applied potential that can be used to produce aluminium
metal? (5 marks)
A typical Hall-Heroult cell for the production of aluminium metal from Al2O3
operates with a current of 100 000 A. What weight of aluminium is produced
in one hour of operation? (7 marks)
(Faraday Constant = 9.65 x 104 C)
INORGAN1J2000 Page 2
Q3 Characterization of Molecular Compounds
Answer TWO parts from part (a), part (b) and part (c).
(a) Outline the three main factors governing absorption intensity in molecular
spectroscopy. (12.5 marks)
(b) Tetrafluorosilane, SiF4 (a tetrahedral molecule) is a gas at ambient temperature
and pressure but is unlikely to be a contributor to the atmospheric greenhouse
effect, due to its hydrolytic lablity. Calculate the number of vibrational modes
expected for SiF4 and sketch them, indicating how many of them are
stretching and how many are bending vibrations. Which of these would you
predict to be infrared active and why?
(12.5 marks)
(c) Predict which of the following nuclear isotopes will have zero, half-integral or
integral nuclear spin: 29Si, 10B, 119Sn, 200Hg. (5 marks)
Sketch (line diagram) the 1H NMR Spectrum expected for 2-bromopropane,
H3CCH(Br)CH3, illustrating the use of chemical shift and spin-spin coupling
constants as characteristic features. (7.5 marks)
INORGAN1J2000 Page 3
Q4 Chemical Bonding
Answer part (a) and TWO from parts (b), (c) or (d)
(a) Show how the VSEPR theory may be used to explain the
shapes of the following molecules:
NH3, CF4, SF4, BrF5, SF6.
(7 marks)
(b) Explain why the bond dissociation energy of N2 is larger than that of
N + but that of O is smaller than that of O +.
2 2 2
(9 marks)
(c) Explain how the Molecular Orbital and Valence Bond theories,
respectively, account for the π-bonding in the ozone molecule, O3,
which has a bent geometry.
(9 marks)
(d) Explain how the Molecular Orbital and Valence Bond theories,
respectively, account for the partial polar character of the I-Cl bond in
iodine monochloride.
(9 marks)
INORGAN1J2000 Page 4
Q5 Co-ordination Chemistry
Answer parts (a) and (b) and EITHER part (c) OR part (d)
(a) For the following compounds, give the oxidation state of the transition
metal and the number of d electrons in the metal's valence shell:
(i) K[MnO4]
(ii) Na2[V(O)(SCN)4]
(iii) ReBr(CO)5
(3 marks)
(b) Use the following examples to illustrate the types of isomerism found
in transition metal complexes:
(i) [Ni(en)3]2+
(ii) Pt2Cl4(PPh3)2
(iii) Cr(NH3)3(NCS)3
(en = ethylenediamine [1,2-diaminoethane])
(9 marks)
(c) When an ethanolic solution of NiBr2 is treated with two equivalents of
the phosphine PEtPh2, two products A and B can be obtained by
varying the crystallisation conditions. Compound A has no dipole
moment and is diamagnetic. One peak due to Ni-Br stretching can be
observed in its IR spectrum. Compound B has a dipole moment and is
paramagnetic. The IR spectrum of B shows two peaks due to Ni-Br
stretching. By contrast, the analogous reaction with PtBr2 and two
equivalents of the same phosphine PEtPh2 gives just one compound, C,
that has similar spectroscopic and magnetic characteristics to A.
Identify A, B and C and explain the observations.
(13 marks)
(d) Discuss stepwise and overall stability constants in transition metal
complexes.
(13 marks)
INORGAN1J2000 Page 5