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BSc and MSci DEGREES AUGUST 2009, for Internal Students of the Imperial College of Science, Technology and Medicine

This paper is also taken for the relevant examination for the Associateship


Monday 17th August 2009, 09.30-12.30

Answer ONE question from each attended course


Year 1/0809

Turn Over

Q1 - Inorganic and Organic Reactivity

Answer THREE of the following: i) Identify the mechanistic type and draw the curly arrows for the following reaction.



[Me3N-OH OH]

(4 marks)

ii) Identify the mechanistic type and draw the curly arrows for the following reaction.



(4 marks)

iii) Give the reaction type and the oxidation states for the metal atoms in the following reaction
I Rh Ph3P I CO Ph3P OC Rh CO PPh3



+ I2

(4 marks)

iv) Give the reaction type and the oxidation states for the metal atoms in the following reaction [CoCl4]2 + 2H2O [CoCl2(H2O)2] + 2Cl

(4 marks)

Q2 Atomic Structure
Answer parts a) AND b) and EITHER part c) OR part d) a) Answer ALL parts of this question. The successive ionisation energies of germanium are shown in the following table: Ionisation energy (kJmol-1) 1st 760 2nd 1540 3rd 3300 4th 4390 5th 8950

i) Identify the sub-level from which the electron is removed when the first ionisation energy of germanium is measured. (1 mark) ii) Write an equation, including state symbols, for the process occurring when measuring the second ionisation energy of germanium. (2 marks) iii) Explain why the difference between the 4th and 5th ionisation energies is much greater than the difference between any other two successive values. (4 marks) b) Answer ALL parts of this question. i) Explain why scandium and zinc are not classified as transition metals. (4 marks) ii) List and rationalise the ground state electronic configurations of chromium and copper. (4 marks) c) Use Slaters Rules to calculate values of Zeff for: (i) a 4s electron in a Vanadium atom (4 marks) AND (ii) a 3d electron in a Vanadium atom. (4 marks) Thereby predict the ground state configuration of the V+ ion. (2 marks)


d) Discuss how the shell and subshell structure of the periodic table may be used to rationalise: (i) the occurrence of the ions Na and Na

(5 marks)

AND (ii) the commonly observed oxidation states of Sn and P. (5 marks)

Q3 - Aromatic Chemistry Aromatic Chemistry: For the synthesis shown below answer TWO of the following questions. i) What are the reagents in step A? ii) What is the structure of compound B? iii) Show the mechanism for the formation of B. (6.5 marks) (6.5 marks) (6.5 marks)

step A


Q4 Chemical Equilibrium
Answer part a) AND EITHER parts b) OR c). a) Answer ALL parts of this question. i) If the equilibrium constant for a reaction at 300 K is 0.01, what is the reaction free energy? (3 marks) If the standard redox potential for a two electron reaction is -0.2 V, what is the corresponding standard free energy change? (3 marks) In thermodynamics, what are meant by the terms state function and path function? Give two examples of each. (3 marks) How does an electrolytic electrochemical cell differ from a galvanic electrochemical cell? (2 marks) Sulfurous acid, H2SO3, is a stronger acid than nitrous acid, HNO2 . Which is the stronger base, HSO3





or NO2 ? (2 marks)

b) Answer ALL parts of this question. i) Distinguish between the Bronsted/Lowry and Lewis definitions of acids and bases. (2 marks) Vinegar is composed of a 0.5 mol dm-3 solution of acetic acid in water. The dissociation constant of acetic acid is 1.76 x 10-5 mol dm-3. ii) iii) Calculate the pH of vinegar. (5 marks) Calculate the pH of a solution containing 0.05 mol dm-3 acetic acid and 0.1 mol dm-3 sodium acetate. (5 marks)


c) Answer ALL parts of this question. Consider the reaction given below: H2 (g) + I2 (s) i) HI(g)

From the thermodynamic data given below, determine the standard reaction enthalpy and entropy. (4 marks) Assuming that the reaction enthalpy and entropy are temperature independent, determine the crossover temperature at which the reactants and products are at equilibrium. Describe the behaviour of the reaction above and below the crossover temperature. (8 marks) Thermodynamic Data: Hfo (HI, g) = 26.48 kJ mol-1 Smo (HI, g) = 206.6 J mol-1 K-1, Smo (H2, g) = 130.7 J mol-1 K-1, Smo (I2, s) = 116.1 J mol-1 K-1


Q5 Introduction to Spectroscopy & Characterisation Prof A de Mello

Answer part (a) and EITHER part (b) OR part (c). (a) Answer ALL parts of this question. (i) The peak of the light emission from a bar of hot iron occurs at 1400 nm. Estimate its temperature. (4 marks) (ii) For O2, values for the =01, 02, 03 transitions are 1556.2, 3088.3 and 4596 cm-1 respectively. Calculate both the anharmonicity constant, xe, (3 marks) and the equilibrium oscillation wavenumber, e. (3 marks) What is the zero point wavenumber for the system? (3 marks) (9 marks) (b) Answer ALL parts of this question. The pure rotational spectrum of 63Cu1H (in the gas phase) consists of equidistant lines spaced 477 GHz apart (i) Determine the rotational constant. Give you answer in units of cm-1. (4 marks) (ii) Using your value of B, determine the equilibrium bond length for 63Cu1H. (6 marks) (iii)Determine the position of the J=10 J=11 transition. Give your answer in units of cm-1. (2 marks) (c) Answer ALL parts of this question. (i) A spectrum consists of a single absorption peak occurring at 4000 cm-1. This is indicative of a transition between what kind of molecular energy states? (2 marks) (ii) The equilibrium oscillation frequency of 23Na1H is 1172 cm-1 and the anharmonicity constant is 0.0168. Determine the position of both the fundamental and first hot band peaks in the infra-red spectrum. How would you confirm the identity of the hot band peak? (10 marks)

Q6 Inorganic Characterisation Dr Charlotte Williams

Answer part (a) and EITHER part (b) OR part (c). (a) Answer ALL parts of this question: (i) Sketch the 31P NMR spectra of trichlorophosphine (PCl3) and phosphorus trihydride (PH3). Indicate the peak multiplicities and chemical shifts in your sketch. [Assume that 31P, I=1/2, 100% abundant, 1H, I=1/2, 100% abundant and all other nuclei are NMR inactive.] (6 marks) Calculate the isotope distribution pattern for the molecular ion of trichlorophosphine (PCl3). Sketch the molecular ion as observed by EI mass spectrometry. [Assume that 31P is 100% abundant; 35Cl is 75% abundant; 37Cl is 25% abundant.] (4 marks) (b) Answer ALL parts of this question: Determine the number of vibrational modes predicted for SO2 and MgCl2. (4 marks) (i) For both SO2 and MgCl2 sketch the vibrational modes. Discuss, for each mode, whether it is IR active or inactive. (8 marks)


Explain why the IR absorptions of SO2 are often observed as a series of closely spaced lines, rather than a single absorption. (3 marks) (c) Answer ALL parts of this question: The UV-Vis spectrum of KMnO4 solution shows an absorbance at 565 nm. (i) State how the absorption can be used to estimate the colour of the KMnO4 solution. What type of molecular transition is involved and what intensity do you associate with such a transition? (5 marks) (ii) How could you use UV-Vis spectroscopy to determine the concentration of an aqueous solution of KMnO4? [Assume that you have some pure KMnO4 available.] (5 marks) (iii) Explain why benzene shows a singlet in the 1H NMR spectrum in the region of 7-8 ppm. Explain these observations. (5 marks)