UNIVERSITY COLLEGE LONDON EXAMINATION FOR INTERNAL STUDENTS MODULE CODE ASSESSMENT PATTERN MODULE NAME LEVEL: DATE TIME CHEM0009 CHEM0009A4UC CHEMO0009 - Basic Physical Chemistry Undergraduate 06/05/2021 14:30 This paper is suitable for candidates who attended classes for this module in the following academic year(s): Year 2020/21 ‘Additional material Special instructions Periodic table.pdf and Physical constants. pdf NIA Exam paper word count NIA TURN ore)CHEM0009 page 2 of 5 Candidates should attempt ALL THREE questions. Each question is marked out of 25 and the numbers in square brackets in the right-hand margin indicate the provisional allocation of marks 10 the subsections of a question. 1, Answer ALL parts, @) (b) (© The photoelectric effect is quantified by the Einstein equation Ym, w-@. (i) Why can the photoelectric effect not be explained by a wave-only model of electromagnetic radiation? (i) A photon of radiation with wavelength 290 nm ejects an electron with a Kinetic energy of 1.81 eV from a metal surface. Determine @ and hence calculate the maximum wavelength (in nm) of radiation capable of ejecting an electron from the metal. Consider a particle confined in a one-dimensional box of length Z which has infinite potential energy barriers at x = 0 and x ~ L. The potential energy inside the box is zero. (i) State the boundary conditions the wavefunction must satisfy. (i) Explain why ¥(x) = Asin(kx)+Beos(kx) cannot be a solution to the Schrédinger equation for this particle if both 4 and B are non-zero constants, (ii) For the wavefunction ¥(x) = Asin (kx), sketch the lowest energy wavefunction and the 4" lowest energy wavefunction showing the position (including the value of x) of any nodes. On the same figure sketeh, [PCof for these two wavefunctions. 4 > (iv) Would the value of [Woofer be different or the same for the two wavefunctions in part (iii)? Explain your reasoning. State, giving your reasons, whether the following functions are satisfactory wavefunctions (well-behaved wavefunctions) for all values of the vatiable x, where 4, B and c are constants. A tan(ex) (ii) Bexp(-ex’) x) (iii) [Question 1 continued overleaf 2] f4] 2]CHEM0009 page 3 of 5 Question I continued] (d) Consider a particle rotating about a fixed point at a distance r (a particle on a ring). The energy levels for the particle are given by E,, =m3h° /27 and the de Broglie wavelength by [2ar/m|. where /is the moment of inertia and m, is a quantum number with values 0,+1,+2,+3, 2. Answer ALL parts. @ (b) (i) Sketch an energy level diagram for m =0,+1, 21 (ii) Explain why the de Broglie wavelength can only take certain values. (21 Calculate the most probable speed and the root mean square speed for hydrogen molecules in a 1 litre glass vessel filled with hydrogen gas at 1 bar and 298 K. Estimate the total collision frequeney for the gas molecules given the collision cross section o(F:) = 0.27 n io] The gas in the vessel in (a) is replaced by a 1:1 mixture by volume of hydrogen and ethene at a total pressure of 1 bar. (i) The rate coefficient for the reaction of hydrogen with ethene was determined experimentally to be & = 1.32 x 107 mot m sat 628 K. Given the activation energy for the reaction E, = 180 kI mol”, calculate the Arhenius pre-exponential factor 4 for this reaction. [3] (ii) Using kinetic theory, calculate the theoretical Arrhenius pre-exponential factor for the reaction of hydrogen with ethene, given the collision eros section between hydrogen and ethene o (FH, C2Hs) = 0.44 nm’. [10] (ii) Comment on the difference between the experimental and theoretical values of the Arrhenius pre-exponential factor and how the theoretical determination may be improved. (3) (iv) Explain how and why the collision frequency of the gas will change as the reaction proceeds. BICHEM0009 page 4 of 5 The graphs shown below are INCORRECT. w (pressure) @) (b) () Q) Qe) é é S solid, slid 8 = tint 3 S é 7 Genperarre) Presse) ra Figure (1) shows the phase diagram of a one-component system. (i) State what is incorrect in the figure and sketch a correct version of this phase diagram. (ii) Indicate the position of the triple point in the phase diagram, and state how triple point is defined in terms of the molar Gibbs energies of the phases. Figure (2) shows how the molar Gibbs energies of the solid and the gas of a material change with pressure. Explain why these trends must be incorrect and draw a correct version of this sketch Figure (3) shows a plot of In(p) against 1/7 where p is the vapour pressure of a solid or liquid, and 7 the temperature of the system. (i) Explain which thermodynamic quantities can be obtained from such a plot by giving the relevant equations. (ii) State why the trend shown is incorrect and sketch a correct version of this, figure. [Question 3 continued overleafCHEM0009 page 5 of 5 Question 3 continued] (d) ‘The equilibrium constant K* of the gas phase reaction C:Ha(g) 2 CoHa(g) + Ho(g) has a value of 0.0501 at a temperature of 900 K. @ 1.00 mol of Hs is injected into an empty reaction chamber. Predict the partial pressures of all three chemical species in equilibrium at a total pressure of 0.100 bar and 900 K. (ii) Calculate the standard reaction Gibbs energy AG? for this reaction at 900 K.. Starting from a reaction mixture under standard conditions, would the forward or reverse reaction be spontaneous? (iii) Define the equilibrium constant for the gas phase reaction 2 C2HA(g) + 2 Hg) 2 2 C2Helg) and calculate its value from the equilibrium constant given above, (iv) The molar heat capacity of C2Hs is given by Cyan / (IK mol") = 14.73 + 0.01272 T/K. Calculate how much heat is required to heat 2.30 mol of C2Hs from 298 K to 900K. END OF PAPER [6]