THE UNIVERSITY OF QUEENSLAND Department of Chemistry Second Semester Examination, November, 2004 DO NOT REMOVE THIS. PAPER FROM THE EXAMINATION ROOM CHEM2056 NNGINEERING CHEMISTRY Time: TWO (2) Hours for working Ten minutes for perusal before examination begins ANSWER QUESTIONS AS INDICATED Answer each section (A & B) in a separate booklet Questions carry the number of marks indicated. Calculators are allowed but no pocket computers or programmable calculators with alpha- numeric capabilities may be used. COPYRIGHT RESERVED2 Second Semester Examination , November, 2004 ~ CHEM2056 Engineering Chemistry _ Section A (40 marks; spend about 40 minutes on this section) A reaction obeys the stoichiometric equation A+2B>2Z Rates of formation of Z at various concentrations of A and B are given in the following table: TAO BIO Rate 35x10" 23x10 5.0x 10 2.0 x 10% 4.0x10° _ 7.0x10? 46x 107 7.0.x 107 9.2.x 10" What are ot and in the rate equation yv=k[AP[B]"? Caleulate the rate constant k. [8 marks] ‘The water flea Daphnia performs a constant number of heartbeats and then dies. The flea lives twice as long at 15 °C than at 25 °C. Calculate the activation energy for the reaction that controls the rate of its heartbeat, [5 marks] For the reaction Cl + CO > COC, the following mechanism has been proposed: a Ch © 2Ck a, ke @Q C+cO © cock Kgs key @) COCI+Ch + COCh+¢l ke (a) Reactions (1) and (2) are very rapid in both directions (rapid pre-equilibria with forward and reverse rate constants ky and ky, and ky and ky for reactions (1) and (2), respectively). ‘The intermediates in this reaction are Cl and COCI. Reaction (3) is much slower and irreversible (rate constant k.). Derive the differential rate law for the formation of COCls. Assuming that the initial concentrations of Cly and CO are the same ({AJo) integrate this rate law. (Hint: Set [COCL] = x and write the concentrations of Cl: and CO in terms of [Alo and x) [15 marks]3 Second Semester Examination, November, 2004 — CHEM2056 Engineering Chemistry 4. ‘The following results were obtained when the rate (v; concentration change per second) of an enzyme reaction was monitored (a) without inhibitor and (b) with inhibitor at a concentration [I] = 15 1M ({S}p is the substrate concentration): (uM) 100. 300 700 1200 1800 a) v (uMs") 0.49) 0.95 13 15 1.6 b) v (uMs"") 0.27 0.52 0.71 0.81 0.86 Is the inhibition competitive, uncompetitive or non-competitive? Evaluate the Michaelis constant (Ky) and the maximum rate Vn. Using the equation below calculate the values for Kic (competitive inhibition constant) and Ky. (uncompetitive inhibition constant). [12 marks} End of Section A4 Second Semester Examination , November, 2004 ~ CHEM2056 Engineering Chemistry Section B (80 marks; spend about 80 minutes on this section) 5. The addition of 5.00 g of a compound to 250 g of naphthalene lowered the freezing point of the solvent by 0.780 K. Calculate the molar mass of the compound. (Note: K; for naphthalene is 6.94 K kg mol") [6 marks} 6. For the phase diagram for a pure substance given below indicate the number of degrees of freedom, F, for the points marked A, B and C (note that C is a region rather than a point). [6 marks} Luis i 7. The normal boiling point of ethylene glycol (CaH¢02) is 197 °C, and its enthalpy of vaporization is 801 J g', Estimate the temperature at which ethylene glycol will boil in a vacuum distillation if the system were maintained at 50 torr. [8 marks} 8. The contact angle of water on clean glass is essentially zero, The capillary rise of a sample of water at 25°C was measured to be 7.36 cm in a capillary of radius 0.20 mm. What is the surface tension of water at that temperature? [6 marks] 9. Caleulate the adsorption in each of the following cases: (a) The slope of a plot of the surface tension of a series of solutions of sodium lauryl sulfate against the natural log of concentration measured at 300 K is -174mN mt (b) A sample of volume 0.30 em? was collected from the surface of a surfactant solution, of area 0.5 m?, The concentration of this sample was compared to that of the bulk, and it was found that the difference was 3.5 mol m? [5 marks each}Second Semester Examination , November, 2004 ~ CHEM2056 Engineering Chemisti 10. W ‘The linear form of the B.| .T. equation is: Pt e-ne n(P°-P) ne Zn PP Data for the adsorption of nitrogen gas on silica, when plotted according to the linear form of the BET equation, give a slope of 319 mol"! and an intercept of 3.35 mol! Calculate the surface area of the sample and, using the customary approximation, calculate the enthalpy of the adsorption of the first layer. The enthalpy of vaporisation of nitrogen at 77 K (the temperature of the experiment) is 5.60 kJ mol and the effective cross-sectional area of a nitrogen molecule is 0.162 nm_. {12 marks} A modified derivation of the Langmuir equation for the adsorption of a gas, A, onto a solid surface in the presence of a second gas, B, gives the result wo ae ny 1+@,P,+a,P, Assuming that this equation holds and the Langmuir-Hinshelwood mechanism is operative, show under which conditions the heterogeneously catalysed reaction A +B — products will (a) obey second order kinetics and (b) become of order ~1 in A [12 marks} Briefly define each of the following terms (a) allotrope (b) variance (©) osmotic pressure (@) surface pressure (©) adsorption [4 marks each] End of paper. Data sheet follows.6 Second Semester Examination , November, 2004 ~ CHEM2056 Engineering Chemistry DATA SHEET. Constants and conversions: R=83141K" mol! 0°C = 273.15 K: 1 torr= 1 mmHg; 1 atm 6.023 x 10° mol" 013 x 10°N 760 torr Molar masses. C 12.01 g mol: H 1.008 g mol! O 16.0 g mol Selected equations: dG =VdP -SdT MRT? oo AHN? PP =2y/r w=cRT a,P, — S++ j summed over all species ne 1+DaP